UV-absorbing polymers and formulations thereof

ABSTRACT

UV-absorbing polymers are provided that have at least one anhydride repeating unit that is covalently attached to at least one UV-absorbing moiety selected from the group consisting of functionalized dibenzoylmethanes, benzophenone sulfonamides, triphenyl triazines, and combinations thereof. Also provided are formulations comprising the UV-absorbing polymers.

This application is the U.S. national stage application filed under 35§U.S.C. 371 claiming benefit to International Patent Application No.PCT/US14/18021, filed Feb. 24, 2014, which is entitled to priority under35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 61/789,582,filed Mar. 15, 2013, each of which applications are incorporated byreference herein in their entireties.

BACKGROUND

Field of the Invention

The invention provides UV-absorbing polymers. The invention furtherprovides a wide variety of formulations comprising the UV-absorbingpolymers.

Description of Related Art

It is now generally accepted that ultraviolet (UV) radiation can be aserious health hazard. Even a limited exposure to solar radiation cancause short- and long-term skin damage, such as erythema, burns,wrinkles, lentigo (“liver spots”), skin cancers, keratotic lesions, andother cellular changes. There is a greater risk for developing suchconditions for those who send prolonged time in the sun, such as fortheir occupation or during recreation.

UV radiation is just one portion of the electromagnetic spectrum withwavelengths from about 100 nm and about 400 nm, and is further dividedinto three subregions. UV-A radiation, from about 320 nm to about 400nm, has the longest wavelength within the UV spectrum, and consequentlyis the least energetic. While UV-A rays can induce skin tanning, theyare liable to induce adverse changes as well, especially in the case ofsensitive skin or of skin which is continually exposed to solarradiation. In particular UV-A rays cause a loss of skin elasticity andthe appearance of wrinkles, leading to premature skin aging. UV-B rayshave shorter wavelengths, from about 290 nm to about 320 nm, and theirhigher energy can cause erythema and skin burns which may be harmful.The third subgroup, UV-C has the shortest wavelengths, from about 200 nmto about 290 nm, and the highest energy. The Earth's ozone layereffectively filters much UV-C radiation from reaching the ground.Nonetheless, UV-C rays can be generated from tanning bed devices.

In addition to harming the skin, UV radiation can injure the hair,resulting in color changes (especially for color-treated hair),embrittlement, and a loss in aesthetics (e.g., shine, manageability).

UV radiation damage is not limited to the skin and hair, as inanimateobjects exposed to solar radiation can experience changes related tocolor, hardness, and structural integrity, which can contribute toaesthetical and functional deterioration. Thus, there is the very realand demanding need for compositions that protect the skin, hair, andobjects from UV rays, especially UV-A and UV-B radiation. Of specialinterest are compositions that provide broad UV-spectrum protection fromboth UV-A and UV-B radiation.

Broadly speaking, para-aminobenzoic acid (PABA) exhibits a common traitshared with many UV absorbers/filters. The molecule possesses bothelectron withdrawing and electron accepting groups, providing resonancedelocalization that coincides with the absorbed energy of UV radiation:

However, PABA is a highly polar molecule, making it water soluble, andgiving it low persistence, meaning that it is not highly retained on theskin after swimming or perspiring. In addition, due to extensiveintermolecular bonding, PABA exists as a solid, which may furthercomplicate its formulation. Thus, there exists the need to improve thepersistence of UV absorbers, especially those that are water-soluble,and to provide formulation flexibility.

UV absorbers may exhibit photolability, in which the absorbed energycauses photodegradation and/or photoreactivity, and thus reduce itsefficacy. Such photolability may result from irreversible isomerisms(i.e., keto-enol tautomerism and cis-trans isomerism), photocleavage,and/or photoaddition, and may be formulation sensitive, (e.g., blends ofavobenzone and octinoxate). Examples of photolabile UV absorber include,without limitation: avobenzone, PABA derivatives, cinnamates, anddibenzoyl methane derivatives, all of which degrades over time, andreduce UV protection. Hence, there exists a need to stabilize UVabsorbers from photodegradative effects.

Additionally, there exists the need to enhance the efficacy of UVabsorbers without increasing their content in the formula, since amaximum addition level frequently is regulated. This efficacy need isespecially important for avobenzone, a highly effective UV-A absorber.Avobenzone is subject to keto-enol isomerization due to formulationdependencies (e.g., solvent, other UV absorbers):

The enol tautomer (left) has its maximum absorbance at 357 nm, whichidentifies it as a UV-A absorber. Unfortunately, avobenzone is subjectto bimolecular reactions (viz, via cleavage mechanisms) that alter themolecule's structure and decrease its effectiveness as an UV absorber.Hence, an effective method is needed for stabilizing labile chromophoreslike avobenzone in order to enhance their efficacy without increasingtheir addition level.

Methods for stabilizing chromophores, and in particular UV absorbers,are known in the prior art. For example, Japanese patent 1971/26,860describes UV stabilizers having amino, hydroxyl, or isocyanate groupsattached to crosslinked polymers, being crosslinked glycidylmethacrylate-divinylbenzene copolymers or crosslinked styrene-maleicanhydride-divinylbenzene copolymers.

U.S. Pat. No. 4,868,246 teaches polymer chemistries having UV absorbersbonded to recurring units:

in the polymer backbone, on grafted side chains, as pendant units, or ascombinations thereof. The group N-G is the residue of a primary amino orhydrazido substituted stabilizer group selected from (a)2-hydroxybenzophenones, (b) 2-(2-hydroxyphenyl)-2H-benzotriazoles, (c)aryl salicylates, or (d) oxalic acid amides. The polymeric stabilizersare directed for use in other polymeric systems which are normallysubject to actinic light degradation, for example polypropylene. Nomention is made of their use in personal care compositions.

A similar approach is taught in U.S. Pat. No. 4,857,596 for thermallystabilizing antioxidants.

Polymer-bound light stabilizers are disclosed in U.S. Pat. No. 4,975,494that are prepared from a preformed polymer having two different types ofreactive groups and a light stabilizer having hydrazido functionality.

U.S. Pat. No. 6,569,531 teaches additive-containing resins having a bi-or multifunctional additive linking a polyester resin with an additive,such as a UV absorber.

U.S. Pat. No. 7,648,697 teaches compounds derived from polyanhydrideresins with film-forming, UV-absorbing, and photostabilizing properties.

Japanese patent 1985/84,378 provides2-hydroxy-4-(2-hydroxyethoxy)benzophenone reacted with maleicanhydride-grafted polyethylene to form a polyethylene-bound2-hydroxybenzophonone semi-ester.

Two radiation-absorbing polymer chemistries are taught in U.S. Pat. No.6,255,405. The '405 patent is directed toward radiation-absorbingcompositions and coatings, particular for “forming a bottomanti-reflective coating upon producing an integrated circuit.” Thepolymeric compositions comprise two recurring units, the first havingthe formula:

wherein R_(a) and R_(b) may be the same or different and representhydrogen, an alkyl group or other organic groups, Ar represents anorganic chromophore, and n represents 0 or an integer of 1 or more; andthe second recurring unit having the formula:

wherein R_(c) and R_(d) may be the same or different and each representshydrogen, an alkyl group, a carboxyl group, or other organic groups, andZ represents hydrogen, a substituted or non-substituted alkoxyl group, asubstituted or non-substituted alkyl group, a halogen atom, —CN, analkylcarbonyloxy group, an imide group, a substituted or non-substitutedcarbamoyl group, a substituted or non-substituted oxycarbonyl group, ora substituted or non-substituted phenyl group.

U.S. Pat. No. 6,492,455 discloses compositions comprising the reactionproduct of a C₆+ alpha olefin/maleic anhydride copolymer with apolyfunctionalized secondary or tertiary amine. The resulting copolymeris an alternating copolymer of an olefinic monomer and a maleicanhydride with a polyfunctionalized secondary or tertiary amine. Usesincludes hair spray and water-proof sunscreen compositions

U.S. Pat. No. 7,361,710 describes compositions comprising the reactionof (a) an unsaturated vegetable oil and an enophile or dienophile havingacid, ester, or anhydride functionality and (b) a functional vinylmonomer. For example, soybean oil is reacted with maleic anhydride, toyield a maleated vegetable oil:

The maleated oil is reacted with hydroxyethyl methacrylate,2-(tert-butylamino)ethyl methacrylate, or glycidyl methacrylate.

Another maleated oil is described in U.S. Pat. No. 3,428,589, which isdirected to polycarboxylic acid anhydride resins of high viscosity, andfor such resins of voltage capabilities. This invention discloses theheating (1) of a dry oil, a modified drying oil, or a mixture thereof,and (2) and alpha, beta-ethylenically unsaturated dicarboxylic acidanhydride, which is heated until a polycarboxylic acid anhydride resinproduct (i.e., an adduct) with a desirably high viscosity is obtained.The polycarboxylic acid anhydride resin is then reacted with an organicaromatic primary or secondary amine, as represented in the followingreaction:

wherein R′ represented the drying oil portion of the adduct, and R″ ishydrogen or alkyl. The '589 patent specifies that the organic aromaticprimary or secondary amine has from 1 to 20 carbon atoms, preferablyfrom 1 to 10 carbon atoms. The '589 patent discloses compositions forelectrocoating baths, compositions with high throwing power, and ofexcellent intermediate voltage capacity.

Additional disclosure related to anhydride-functionalized vegetable oilsis provided by Aydin, S., et al., Prog Org Coat, 51, 273-279, 2004; andby Guner, F. S., et al., Prog Polym Sci, 31, 633-670, 2006, both ofwhich are incorporated in their entirety by reference. While these worksdescribe methods to graft anhydride functional groups onto vegetableoils, they do not teach subsequent grafting of UV absorbers onto theanhydride moiety.

Functionalized poly(alpha olefin-maleic anhydride) polymers are thesubject of application WO 2007/096400A1. This functionalized copolymerhas the structure:

wherein X is —O— or —NH—, and —X—R₂— is a functional radical selectedfrom a group that includes natural molecules that are UV absorbers, suchas tannins, flavonoids, thymol, caffeic acid esters, and vitamin E.

UV absorbers bound to polymers in personal care compositions are taughtin US 2010/0189661, the contents of which are incorporated in theirentirety by reference.

Despite advances in UV-absorbers, there remains a commercial demand forUV-absorbing polymers with enhanced performance.

SUMMARY

In one aspect, the invention provides UV-absorbing polymers. In a firstembodiment, a UV-absorbing polymer comprises a first repeating unitselected from the group consisting of:

and combinations thereof, wherein each X is independently selected fromthe group consisting of O, NR₁, and combinations thereof; each R₁ and R₂is independently selected from the group consisting of hydrogen,halogen, and functionalized and unfunctionalized hydrocarbyl optionallyhaving one or more heteroatoms; each R₃ is independently selected fromthe group consisting of hydrogen, U, and functionalized andunfunctionalized hydrocarbyl optionally having one or more heteroatoms;each M is independently selected from the group consisting of alkalimetal ion, alkaline earth metal ion, ammonium ion, and combinationsthereof; each U has a structure independently selected from the groupconsisting of:

and combinations thereof, wherein each R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₄₁,R₄₂, R₄₃, R₄₄ and R₄₅ is independently selected from the groupconsisting of hydrogen, halogen, amino, alkyl amino, hydroxyl, alkoxyl,sulfonyl, carboxyl, functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms, and combinations thereof;each Y is independently selected from the group consisting of O, NR₁, S,and combinations thereof; each Q is independently selected from thegroup consisting of functionalized and unfunctionalized hydrocarbyleneoptionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for each U.

In a second embodiment, a UV-absorbing polymer comprises a firstrepeating unit selected from the group consisting of:

and combinations thereof, wherein each X is independently selected fromthe group consisting of O, NR₁, and combinations thereof; each R₁ and R₂is independently selected from the group consisting of hydrogen,halogen, and functionalized and unfunctionalized hydrocarbyl optionallyhaving one or more heteroatoms; each R₃ is independently selected fromthe group consisting of hydrogen, U, and functionalized andunfunctionalized hydrocarbyl optionally having one or more heteroatoms;each M is independently selected from the group consisting of alkalimetal ion, alkaline earth metal ion, ammonium ion, and combinationsthereof; each U has a structure independently selected from the groupconsisting of:

and combinations thereof, wherein each R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₂₁,R₂₂, R₂₃, R₂₄ and R₂₅ is independently selected from the groupconsisting of hydrogen, halogen, amino, alkyl amino, hydroxyl, alkoxyl,sulfonyl, carboxyl, functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms, and combinations thereof;each Y is independently selected from the group consisting of O, NR₁, S,and combinations thereof; each Q is independently selected from thegroup consisting of functionalized and unfunctionalized hydrocarbyleneoptionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for each U.

In a third embodiment, a UV-absorbing polymer comprises a firstrepeating unit selected from the group consisting of:

and combinations thereof, wherein each X is independently selected fromthe group consisting of O, NR₁, and combinations thereof; each R₁ and R₂is independently selected from the group consisting of hydrogen,halogen, and functionalized and unfunctionalized hydrocarbyl optionallyhaving one or more heteroatoms; each R₃ is independently selected fromthe group consisting of hydrogen, U, and functionalized andunfunctionalized hydrocarbyl optionally having one or more heteroatoms;each M is independently selected from the group consisting of alkalimetal ion, alkaline earth metal ion, ammonium ion, and combinationsthereof; each U has a structure independently selected from the groupconsisting of:

and combinations thereof, wherein each R₁₂, R₁₃, R₁₅, R₁₆, R₂₂, R₂₄,R₂₅, R₃₂, R₃₄ and R₃₅ is independently selected from the groupconsisting of hydrogen, halogen, amino, alkyl amino, hydroxyl, alkoxyl,sulfonyl, carboxyl, functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms, and combinations thereof;each Y is independently selected from the group consisting of O, NR₁, S,and combinations thereof; each Q is independently selected from thegroup consisting of functionalized and unfunctionalized hydrocarbyleneoptionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for each U.

In a fourth embodiment, a UV-absorbing polymer comprises a firstrepeating unit selected from the group consisting of:

and combinations thereof, wherein each X is independently selected fromthe group consisting of O, NR₁, and combinations thereof; each R₁ and R₂is independently selected from the group consisting of hydrogen,halogen, and functionalized and unfunctionalized hydrocarbyl optionallyhaving one or more heteroatoms; R₃ is selected from the group consistingof hydrogen, U, and functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms; M is independently selectedfrom the group consisting of alkali metal ion, alkaline earth metal ion,ammonium ion, and combinations thereof; each U has a structureindependently selected from the group consisting of:

and combinations thereof, wherein each R₁₂, R₁₃, R₁₅, and R₁₆ isindependently selected from the group consisting of hydrogen, halogen,amino, alkyl amino, hydroxyl, alkoxyl, sulfonyl, carboxyl,functionalized and unfunctionalized hydrocarbyl optionally having one ormore heteroatoms, and combinations thereof; each R₅ is independentlyselected from the group consisting of hydrogen and functionalized andunfunctionalized hydrocarbyl optionally having one or more heteroatoms;each R₆ and R₇ is independently selected from the group consisting offunctionalized and unfunctionalized hydrocarbyl optionally having one ormore heteroatoms; each Q is independently selected from the groupconsisting of functionalized and unfunctionalized hydrocarbyleneoptionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for each U.

In another aspect, the invention provides a wide variety of formulationscomprising the UV-absorbing polymers described herein. Such formulationsinclude, but are not limited to personal care (e.g., hair care, suncare, sunscreen, skin care, color cosmetic, and oral care) formulations,adhesives, coatings, paints, electronics, Household, Industrial andInstitutional (HI&I) formulations, inks, membranes, metal workingfluids, oilfield formulations, plastics and plasticizers, paper,construction formulations, textiles, industrial products, biocides,pharmaceuticals, food, and agrochemical formulations.

DETAILED DESCRIPTION

The terms “ultraviolet” and “UV” are taken to mean electromagneticradiation, especially solar electromagnetic radiation, with a wavelengthfrom about 100 nm to about 400 nm, and includes the UV-A, UV-B, and UV-Csub-classifications of such radiation.

The term “UV-A” means ultraviolet electromagnetic radiation with awavelength from about 320 nm to about 400 nm, and includes UV-A1 (fromabout 340 nm to about 400 nm) and UV-A2 (from about 320 nm to about 340nm).

The term “UV-B” means ultraviolet electromagnetic radiation with awavelength from about 290 nm to about 320 nm.

The term “UV-C” means ultraviolet electromagnetic radiation with awavelength from about 200 nm to about 290 nm.

The term “UV-absorber” is taken to mean a chemical entity that absorbs,scatters, and/or reflects UV radiation.

The term “each independently selected from the group consisting of”means when a group appears more than once in a structure, that group maybe selected independently each time it appears.

The term “functionalized” refers to replacing one or more hydrogens withone or more non-hydrogen groups, for e.g., alkyl, alkoxyl, cycloalkyl,alkenyl, cycloalkenyl, alkynyl, and/or aryl groups. Alkyl, alkenyland/or alkynyl groups include C₁-C₆₀, more particularly C₁-C₃₆, and mostparticularly C₁-C₁₈ groups. Cycloalkyl groups include cyclopentane,cyclohexane, cycloheptane, and the like. Alkoxy groups include methoxy,ethoxy, n-propoxy, isopropoxy, and the like. Aryl groups includebenzenes, naphthalenes (2 rings), anthracenes (3 rings), and the like.

The term “hydrocarbyl” refers to straight-chain and/or branched-chaingroups comprising carbon and hydrogen atoms with optional heteroatom(s).Particularly, the hydrocarbyl group includes C₁-C₆₀, more particularlyC₁-C₃₆, and most particularly C₁-C₁₈ alkyl and alkenyl groups optionallyhaving one or more hetero atoms. The hydrocarbyl group may be mono-, di-or polyvalent. The divalent hydrocarbyl group is termed as“hydrocarbylene”.

The term “heteroatom” refers to oxygen, nitrogen, sulfur, silicon,and/or phosphorous. The heteroatom may be present as a part of one ormore functional groups on the hydrocarbyl chain and/or as a part of thehydrocarbyl chain itself.

The term “halogen” refers to chloro, bromo, iodo and/or fluoro.

The term “residue of” refers to a fragment of a reactant that remainsafter a reaction with another reactant(s). The residue may be mono-, di-or polyvalent.

The term “lower molecular weight alcohol” refers to any alcohol havingfrom one to 4 carbon atoms, and includes: methanol, ethanol, 1-propanol,2-propanol, allyl alcohol, propargyl alcohol, 2-aminoethanol, ethyleneglycol, methylpropargyl alcohol, 1-butyn-4-ol, 2-butyn-1-ol,2-buten-1-ol, 2-butanol, 2-methyl-2-propanol, and t-butanol. In variousaspects of the invention the lower molecular weight alcohol may bemethanol, ethanol, 1-propanol, 2-propanol, and t-butanol.

The term “monomer” refers to a small molecule that chemically bondsduring polymerization to one or more monomers of the same or differentkind to form a polymer.

The term “polymer” refers to a large molecule comprising one or moretypes of monomer residues (repeating units) connected by covalentchemical bonds. By this definition polymer encompasses molecules whereinthe number of monomer units ranges from very few, which more commonlymay be called oligomers, to very many. Non-limiting examples of polymersinclude homopolymers, non-homopolymers, copolymers, terpolymers,tetramers, and the like, wherein the polymer may be a random, block, oralternating polymer.

The term “homopolymer” refers to a polymer that consists essentially ofa single monomer type.

The term “non-homopolymer” refers to a polymer that comprises more thanone monomer types.

The term “copolymer” refers to a non-homopolymer that comprises twodifferent monomer types.

The term “terpolymer” refers to a non-homopolymer that comprises threedifferent monomer types.

The term “branched” refers to any non-linear molecular structure. Toavoid any arbitrary delineation, the term “branched” describes bothbranched and hyperbranched structures.

The term “polymer-bound UV absorber” refers to a polymer molecule havingat least one UV absorber covalently-bonded to the polymer backboneand/or side chain.

The term “free radical addition polymerization initiator” refers to acompound used in a catalytic amount to initiate a free radical additionpolymerization. The choice of initiator depends mainly upon itssolubility and its decomposition temperature.

The term “1-(4-hydroxyphenyl)-3-(4-methylphenyl)-1,3-propanedione,” alsoknown as “JT-benzone” refers to a compound having the structure:

The term “1-(4-hydroxyethylphenyl)-3-(4-methylphenyl)-1,3-propanedione,”also known as “HE-JT benzone,” refers to a compound having thestructure:

The term “577-sulfanamide-ethanolamine” refers to a compound having thestructure:

The term “577-sulfanamide-propylenediamine” refers to a compound havingthe structure:

The term “577-sulfanamide-hexylenediamine” refers to a compound havingthe structure:

The term “p-dimethylaminobenzamido ethanolamine,” which is abbreviatedas DMABEA, refers to a compound having the structure:

The term “p-dimethylaminobenzyl propylenediamine,” which is abbreviatedas DMABPD, refers to a compound having the structure:

The term “p-dimethylaminobenzamido hexylenediamine” which is abbreviatedas DMABHD, refers to a compound having the structure:

The terms “personal care formulation” and “cosmetics” refer tocompositions intended for use on or in the human body, such as skin,sun, oil, hair, cosmetic, and preservative compositions, including thoseto alter the color and appearance of the skin and hair. Potentialpersonal care compositions include, but are not limited to, compositionsfor increased flexibility in styling, durable styling, increasedhumidity resistance for hair, skin, and color cosmetics, sun carewater-proof/resistance, wear-resistance, and thermalprotecting/enhancing compositions.

The term “sun-care formulation” means personal care and/orpharmaceutical compositions and formulations comprising an effectiveamount of UV-absorber. Sun-care formulations include beach and non-beachproducts that are applied to the face, décolleté, lips, and skin totreat and/or protect against erythema, burns, wrinkles, lentigo (“liverspots”), skin cancers, keratotic lesions, and cellular changes of theskin; and to hair to treat and/or protect against color changes, lack ofluster, tangles, split ends, unmanageability, and embrittlement.

The term “performance chemicals formulation” refers to any non-personalcare formulation. Performance chemicals formulations serve a broadspectrum of arts, and include non-limiting compositions such as:adhesives, agricultural, biocides, coatings, electronics,household-industrial-institutional (HI&I), inks, membranes, metalfluids, oilfield, paper, paints, plastics, printing, construction, andwood-care formulations.

The term “oilfield formulation” refers to a composition that may be usedin the exploration, extraction, recovery, or completion of anyhydrocarbon-based fuel. Non-limiting examples of oilfield formulationsinclude anti-agglomerants, emulsifiers, de-emulsifiers, gas hydrateinhibitors, kinetic hydrate inhibitors, shale swelling inhibitors,drilling fluids, drilling muds, friction reducers, rheology modifier,fracturing fluids, and/or scale inhibitors.

The term “coating formulation” refers to any composition suitable forapplication on a substrate in order to provide one or more desiredfunctions, including, but not limited to protecting, smoothing,strengthening, decorating, color enhancing/altering, substrate preparingand/or texturizing. The substrate for a coating formulation may include,without limitation, paper, paper board, wood, inorganic substrate, wovenand non-woven textiles, metal, leather, powder, plastic, polymer, glass,cement, ceramic, traffic, tile, rubber, sealant, cable, concrete,plasterboard, adhesives, fillers, primers, inks, fertilizers,pharmaceuticals, structural materials, molding, printing, inks, and thelike. Examples of coating formulations include, without limitation, thefollowing: paints, primers, stains, sealers, varnishes/polyurethanes,adhesives, waterproofers, wood hardeners. Coating formulations may beapplied by brush, dauber, roll, strip/sheet, and/or trowel, or may beatomized and applied as a spray, mist, or droplet.

A “paint formulation” is a non-limiting, specific type of a “coatingformulation”. Paints may be water based or non-water based (i.e.,solvent based). Paint formulations may be designed for any number ofsubstrates, including wood, siding, dry wall, plaster, plastics,masonry, brick, tile, particle board, glass, stucco, concrete, and thelike. Non-limiting examples of paints include exterior paints, interiorpaints, architectural paints, and automotive paints.

All percentages, ratio, and proportions used herein are based on aweight basis unless other specified.

In a first embodiment, the invention provides a UV-absorbing polymercomprising a first repeating unit selected from the group consisting of:

and combinations thereof, wherein each X may be independently selectedfrom the group consisting of O, NR₁, and combinations thereof; each R₁and R_(2 may be) independently selected from the group consisting ofhydrogen, halogen, and functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms; each R₃ may be independentlyselected from the group consisting of hydrogen, U, and functionalizedand unfunctionalized hydrocarbyl optionally having one or moreheteroatoms; each M may be independently selected from the groupconsisting of alkali metal ion, alkaline earth metal ion, ammonium ion,and combinations thereof; each U has a structure independently selectedfrom the group consisting of:

and combinations thereof, wherein each R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₄₁,R₄₂, R₄₃, R₄₄ and R₄₅ may be independently selected from the groupconsisting of hydrogen, halogen, amino, alkyl amino, hydroxyl, alkoxyl,sulfonyl, carboxyl, functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms, and combinations thereof;each Y may be independently selected from the group consisting of O,NR₁, S, and combinations thereof; each Q may be independently selectedfrom the group consisting of functionalized and unfunctionalizedhydrocarbylene optionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for each U.

Particularly, a first repeating unit may be selected from the groupconsisting of:

and combinations thereof, wherein each Z may be a residue of a monomerindependently selected from the group consisting of functionalized andunfunctionalized: alpha-olefins, maleimides, maleamic acids, maleicanhydride, 4-vinyl-1,2,3-triazoles, 5-vinyl-1,2,3-triazoles,(meth)acrylamides, (meth)acrylates, vinyls, allyls, α-β-olefinicallyunsaturated carboxylic nitriles, styrenes, vinyl ethers, vinyl esters,vinyl acetates, vinyl amides, vinyl alcohols, vinyl carbonates, vinylcarbamates, vinyl thiocarbamates, vinyl ureas, vinyl halides, vinylimidazoles, vinyl lactams, vinyl pyridines, vinyl silanes, vinylsiloxanes, vinyl sulfones, allyl ethers, and combinations thereof, andwherein X, Y, Q, R₁, R₂, R₃, M, U, R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₄₁, R₄₂,R₄₃, R₄₄, and R₄₅ retain the aforementioned definitions.

Non-limiting examples of vinyl ethers include one or more alkyl vinylethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinylether, octyl vinyl ether, ethyl hexyl vinyl ether, decyl vinyl ether,dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether,octadecyl vinyl ether, and combinations thereof.

Non-limiting examples of alpha-olefins include isobutylene, styrene,octadecene, and combinations thereof.

In a particular embodiment, Q may be a C₁-C₆₀ alkylene. Moreparticularly, Q may be a residue of a compound selected from the groupconsisting of diols, diamines, thio alcohols, amino alcohols, polyols,polyether polyols, polyacetal polyethers, polyalkylene polyamines,polyetheramines, polyalkylene imines, polysaccharides, and combinationsthereof. Even more particularly, Q may be a residue of a diol, an aminoalcohol, or a diamine.

Non-limiting examples of diols include ethylene glycol, propyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol,dipropylene glycol, 2-butyl-2-ethyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 1,1-bis(hydroxymethyl)cyclopropane,1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol,1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-pentanediol,1,5-pentanediol, 1,5-pentanediol, 2,4-pentanediol,3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2,5-hexanediol, 1,8-octanediol, and 3,6-dithiaoctane-1,8-diol.

Non-limiting examples of amino alcohols include ethanol amine, propanolamine, 2-(methylamino)ethanol, 1-amino-2-propanol,2-(ethylamino)ethanol, 2-amino-2-methyl-1-propanol, 4-amino-1-butanol,4-amino-2-butanol, 2-(2-aminoethoxy)ethanol, 2-aminocyclopentanol,2-(isopropylamino)ethanol, 2-amino-3-methyl-1-butanol,5-amino-1-pentanol, 2-amino-1-pentanol, 1-amino-1-cyclopentanemethanol,2-aminocyclohexanol, 4-aminocyclohexanol, 6-amino-1-hexanol,2-amino-1-hexanol, 2-(aminomethyl)cyclohexanol,5-amino-2,2-dimethylpentanol, 2-amino-1-phenylethanol,4-chlorophenylalaninol, 2-benzylaminoethanol, 6-amino-1-hexanol,8-amino-1-octanol, and 3-amino-1-adamantanol.

Non-limiting examples of diamines include ethylene diamine,diphenylethylenediamine, 1,3-diaminopropane, diaminocyclopropane,1,4-diaminobutane, 1,5-diaminopentane, diaminocyclopentane,hexamethylenediamine, and diaminocyclohexane.

Particularly, a U group has a structure independently selected from thegroup consisting of:

and combinations thereof, wherein each

(wavy bond) indicates the point of attachment for each U.

In a second embodiment, the invention provides a UV-absorbing polymercomprising a first repeating unit selected from the group consisting of:

and combinations thereof, wherein each X may be independently selectedfrom the group consisting of O, NR₁, and combinations thereof; each R₁and R₂ may be independently selected from the group consisting ofhydrogen, halogen, and functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms; each R₃ is independentlyselected from the group consisting of hydrogen, U, and functionalizedand unfunctionalized hydrocarbyl optionally having one or moreheteroatoms; each M may be independently selected from the groupconsisting of alkali metal ion, alkaline earth metal ion, ammonium ion,and combinations thereof; each U has a structure independently selectedfrom the group consisting of:

and combinations thereof, wherein each R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₂₁,R₂₂, R₂₃, R₂₄ and R₂₅ may be independently selected from the groupconsisting of hydrogen, halogen, amino, alkyl amino, hydroxyl, alkoxyl,sulfonyl, carboxyl, functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms, and combinations thereof;each Y may be independently selected from the group consisting of O,NR₁, S, and combinations thereof; each Q may be independently selectedfrom the group consisting of functionalized and unfunctionalizedhydrocarbylene optionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for U.

Particularly, the first repeating unit may be selected from the groupconsisting of:

and combinations thereof, wherein each Z may be a residue of a monomerindependently selected from the group consisting of functionalized andunfunctionalized: alpha-olefins, maleimides, maleamic acids, maleicanhydride, 4-vinyl-1,2,3-triazoles, 5-vinyl-1,2,3-triazoles,(meth)acrylamides, (meth)acrylates, vinyls, allyls, α-β-olefinicallyunsaturated carboxylic nitriles, styrenes, vinyl ethers, vinyl esters,vinyl acetates, vinyl amides, vinyl alcohols, vinyl carbonates, vinylcarbamates, vinyl thiocarbamates, vinyl ureas, vinyl halides, vinylimidazoles, vinyl lactams, vinyl pyridines, vinyl silanes, vinylsiloxanes, vinyl sulfones, allyl ethers, and combinations thereof, andwherein X, Y, Q, R₁, R₂, R₃, M, U, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₂₁, R₂₂,R₂₃, R₂₄ and R₂₅ retain the aforementioned definitions.

Non-limiting examples of vinyl ethers include one or more alkyl vinylethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinylether, octyl vinyl ether, ethyl hexyl vinyl ether, decyl vinyl ether,dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether,octadecyl vinyl ether, and combinations thereof.

Non-limiting examples of alpha-olefins include isobutylene, styrene,octadecene, and combinations thereof.

In a particular embodiment, Q may be a C₁-C₆₀ alkylene. Moreparticularly, Q may be a residue of a compound selected from the groupconsisting of diols, diamines, thio alcohols, amino alcohols, polyols,polyether polyols, polyacetal polyethers, polyalkylene polyamines,polyetheramines, polyalkylene imines, polysaccharides, and combinationsthereof. Even more particularly, Q may be a residue of a diol, an aminoalcohol, or a diamine.

Non-limiting examples of diols include ethylene glycol, propyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol,dipropylene glycol, 2-butyl-2-ethyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 1,1-bis(hydroxymethyl)cyclopropane,1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol,1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-pentanediol,1,5-pentanediol, 1,5-pentanediol, 2,4-pentanediol,3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2,5-hexanediol, 1,8-octanediol, and 3,6-dithiaoctane-1,8-diol.

Non-limiting examples of amino alcohols include ethanol amine, propanolamine, 2-(methylamino)ethanol, 1-amino-2-propanol,2-(ethylamino)ethanol, 2-amino-2-methyl-1-propanol, 4-amino-1-butanol,4-amino-2-butanol, 2-(2-aminoethoxy)ethanol, 2-aminocyclopentanol,2-(isopropylamino)ethanol, 2-amino-3-methyl-1-butanol,5-amino-1-pentanol, 2-amino-1-pentanol, 1-amino-1-cyclopentanemethanol,2-aminocyclohexanol, 4-aminocyclohexanol, 6-amino-1-hexanol,2-amino-1-hexanol, 2-(aminomethyl)cyclohexanol,5-amino-2,2-dimethylpentanol, 2-amino-1-phenylethanol,4-chlorophenylalaninol, 2-benzylaminoethanol, 6-amino-1-hexanol,8-amino-1-octanol, and 3-amino-1-adamantanol.

Non-limiting examples of diamines include ethylene diamine,diphenylethylenediamine, 1,3-diaminopropane, diaminocyclopropane,1,4-diaminobutane, 1,5-diaminopentane, diaminocyclopentane,hexamethylenediamine, and diaminocyclohexane.

Particularly, a U group has a structure independently selected from thegroup consisting of:

and combinations thereof, wherein each

(wavy bond) indicates the point of attachment for each U.

In a third embodiment, the invention provides a UV-absorbing polymercomprising a first repeating unit selected from the group consisting of:

and combinations thereof, wherein each X may be independently selectedfrom the group consisting of O, NR₁, and combinations thereof; each R₁and R₂ may be independently selected from the group consisting ofhydrogen, halogen, and functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms; each R₃ may be independentlyselected from the group consisting of hydrogen, U, and functionalizedand unfunctionalized hydrocarbyl optionally having one or moreheteroatoms; each M may be independently selected from the groupconsisting of alkali metal ion, alkaline earth metal ion, ammonium ion,and combinations thereof; each U has a structure independently selectedfrom the group consisting of:

and combinations thereof, wherein each R₁₂, R₁₃, R₁₅, R₁₆, R₂₂, R₂₄,R₂₅, R₃₂, R₃₄ and R₃₅ may be independently selected from the groupconsisting of hydrogen, halogen, amino, alkyl amino, hydroxyl, alkoxyl,sulfonyl, carboxyl, functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms, and combinations thereof;each Y may be independently selected from the group consisting of O,NR₁, S, and combinations thereof; each Q may be independently selectedfrom the group consisting of functionalized and unfunctionalizedhydrocarbylene optionally having one or more heteroatoms; and whereineach

(wavy bond) indicates the point of attachment for U.

Particularly, the first repeating unit may be selected from the groupconsisting of:

and combinations thereof, wherein each Z may be a residue of a monomerindependently selected from the group consisting of functionalized andunfunctionalized: alpha-olefins, maleimides, maleamic acids, maleicanhydride, 4-vinyl-1,2,3-triazoles, 5-vinyl-1,2,3-triazoles,(meth)acrylamides, (meth)acrylates, vinyls, allyls, α-β-olefinicallyunsaturated carboxylic nitriles, styrenes, vinyl ethers, vinyl esters,vinyl acetates, vinyl amides, vinyl alcohols, vinyl carbonates, vinylcarbamates, vinyl thiocarbamates, vinyl ureas, vinyl halides, vinylimidazoles, vinyl lactams, vinyl pyridines, vinyl silanes, vinylsiloxanes, vinyl sulfones, allyl ethers, and combinations thereof, andwherein X, Y, Q, R₁, R₂, R₃, M, U, R₁₂, R₁₃, R₁₅, R₁₆, R₂₂, R₂₄, R₂₅,R₃₂, R₃₄ and R₃₅ retain the aforementioned definitions.

Non-limiting examples of vinyl ethers include one or more alkyl vinylethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinylether, octyl vinyl ether, ethyl hexyl vinyl ether, decyl vinyl ether,dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether,octadecyl vinyl ether, and combinations thereof.

Non-limiting examples of alpha-olefins include isobutylene, styrene,octadecene, and combinations thereof.

In a particular embodiment, Q may be C₁-C₆₀ alkylene. More particularly,Q may be a residue of a compound selected from the group consisting ofdiols, diamines, thio alcohols, amino alcohols, polyols, polyetherpolyols, polyacetal polyethers, polyalkylene polyamines,polyetheramines, polyalkylene imines, polysaccharides, and combinationsthereof. Even more particularly, Q may be a residue of a diol, an aminoalcohol, or a diamine.

Non-limiting examples of diols include ethylene glycol, propyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol,dipropylene glycol, 2-butyl-2-ethyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 1,1-bis(hydroxymethyl)cyclopropane,1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol,1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-pentanediol,1,5-pentanediol, 1,5-pentanediol, 2,4-pentanediol,3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2,5-hexanediol, 1,8-octanediol, and 3,6-dithiaoctane-1,8-diol.

Non-limiting examples of amino alcohols include ethanol amine, propanolamine, 2-(methylamino)ethanol, 1-amino-2-propanol,2-(ethylamino)ethanol, 2-amino-2-methyl-1-propanol, 4-amino-1-butanol,4-amino-2-butanol, 2-(2-aminoethoxy)ethanol, 2-aminocyclopentanol,2-(isopropylamino)ethanol, 2-amino-3-methyl-1-butanol,5-amino-1-pentanol, 2-amino-1-pentanol, 1-amino-1-cyclopentanemethanol,2-aminocyclohexanol, 4-aminocyclohexanol, 6-amino-1-hexanol,2-amino-1-hexanol, 2-(aminomethyl)cyclohexanol,5-amino-2,2-dimethylpentanol, 2-amino-1-phenylethanol,4-chlorophenylalaninol, 2-benzylaminoethanol, 6-amino-1-hexanol,8-amino-1-octanol, and 3-amino-1-adamantanol.

Non-limiting examples of diamines include ethylene diamine,diphenylethylenediamine, 1,3-diaminopropane, diaminocyclopropane,1,4-diaminobutane, 1,5-diaminopentane, diaminocyclopentane,hexamethylenediamine, and diaminocyclohexane.

Particularly, each U group has an independently selected structure:

wherein

(wavy bond) indicates the point of attachment for U.

In a fourth embodiment, the invention provides a UV-absorbing polymercomprising a first repeating unit selected from the group consisting of:

and combinations thereof, wherein each X may be independently selectedfrom the group consisting of O, NR₁, and combinations thereof; each R₁and R₂ may be independently selected from the group consisting ofhydrogen, halogen, and functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms; R₃ may be selected from thegroup consisting of hydrogen, U and functionalized and unfunctionalizedhydrocarbyl optionally having one or more heteroatoms; M may beindependently selected from the group consisting of alkali metal ion,alkaline earth metal ion, ammonium ion, and combinations thereof; each Uhas a structure independently selected from the group consisting of:

and combinations thereof, wherein each R₁₂, R₁₃, R₁₅, and R₁₆ may beindependently selected from the group consisting of hydrogen, halogen,amino, alkyl amino, hydroxyl, alkoxyl, sulfonyl, carboxyl,functionalized and unfunctionalized hydrocarbyl optionally having one ormore heteroatoms, and combinations thereof; each R₅ may be independentlyselected from the group consisting of hydrogen and functionalized andunfunctionalized hydrocarbyl optionally having one or more heteroatoms;each R₆ and R₇ may be independently selected from the group consistingof functionalized and unfunctionalized hydrocarbyl optionally having oneor more heteroatoms; each Q may be independently selected from the groupconsisting of functionalized and unfunctionalized hydrocarbyleneoptionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for U.

Particularly, the first repeating unit may be selected from the groupconsisting of:

and combinations thereof, wherein each Z may be a residue of a monomerindependently selected from the group consisting of functionalized andunfunctionalized: alpha-olefins, maleimides, maleamic acids, maleicanhydride, 4-vinyl-1,2,3-triazoles, 5-vinyl-1,2,3-triazoles,(meth)acrylamides, (meth)acrylates, vinyls, allyls, α-β-olefinicallyunsaturated carboxylic nitriles, styrenes, vinyl ethers, vinyl esters,vinyl acetates, vinyl amides, vinyl alcohols, vinyl carbonates, vinylcarbamates, vinyl thiocarbamates, vinyl ureas, vinyl halides, vinylimidazoles, vinyl lactams, vinyl pyridines, vinyl silanes, vinylsiloxanes, vinyl sulfones, allyl ethers, and combinations thereof, andwherein X, Q, R₁, R₂, R₃, M, U, R₁₂, R₁₃, R₁₅, R₁₆, R₅, R₆, and R₇retain the aforementioned definitions.

Non-limiting examples of vinyl ethers include one or more alkyl vinylethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinylether, octyl vinyl ether, ethyl hexyl vinyl ether, decyl vinyl ether,dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether,octadecyl vinyl ether, and combinations thereof.

Non-limiting examples of alpha-olefins include isobutylene, styrene,octadecene, and combinations thereof.

In a particular embodiment, Q may be C₁-C₆₀ alkylene. More particularly,Q may be a residue of a compound selected from the group consisting ofdiols, diamines, thio alcohols, amino alcohols, polyols, polyetherpolyols, polyacetal polyethers, polyalkylene polyamines,polyetheramines, polyalkylene imines, polysaccharides, and combinationsthereof. Even more particularly, Q may be a residue of a diol, an aminoalcohol, or a diamine.

Non-limiting examples of diols include ethylene glycol, propyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol,dipropylene glycol, 2-butyl-2-ethyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 1,1-bis(hydroxymethyl)cyclopropane,1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol,1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-pentanediol,1,5-pentanediol, 1,5-pentanediol, 2,4-pentanediol,3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2,5-hexanediol, 1,8-octanediol, and 3,6-dithiaoctane-1,8-diol.

Non-limiting examples of amino alcohols include ethanol amine, propanolamine, 2-(methylamino)ethanol, 1-amino-2-propanol,2-(ethylamino)ethanol, 2-amino-2-methyl-1-propanol, 4-amino-1-butanol,4-amino-2-butanol, 2-(2-aminoethoxy)ethanol, 2-aminocyclopentanol,2-(isopropylamino)ethanol, 2-amino-3-methyl-1-butanol,5-amino-1-pentanol, 2-amino-1-pentanol, 1-amino-1-cyclopentanemethanol,2-aminocyclohexanol, 4-aminocyclohexanol, 6-amino-1-hexanol,2-amino-1-hexanol, 2-(aminomethyl)cyclohexanol,5-amino-2,2-dimethylpentanol, 2-amino-1-phenylethanol,4-chlorophenylalaninol, 2-benzylaminoethanol, 6-amino-1-hexanol,8-amino-1-octanol, and 3-amino-1-adamantanol.

Non-limiting examples of diamines include ethylene diamine,diphenylethylenediamine, 1,3-diaminopropane, diaminocyclopropane,1,4-diaminobutane, 1,5-diaminopentane, diaminocyclopentane,hexamethylenediamine, and diaminocyclohexane.

Particularly, a U group has a structure independently selected from thegroup consisting of:

and combinations thereof, wherein each

(wavy bond) indicates the point of attachment for U.

The first repeating unit of UV-absorbing polymers described herein maybe a residue of an anhydride monomer that may be functionalized by oneor more UV-absorbing compound(s). Particularly, the anhydride monomerprior to functionalization may be selected from the group consisting ofmaleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride,itaconic anhydride, citraconic anhydride, chloromaleic anhydride,bromomaleic anhydride, dichloromaleic anhydride, dibromomaleicanhydride, phenylmaleic anhydride, and combinations thereof. Thefunctionalization of anhydride monomers by one or more UV-absorbingcompound(s) results in formation of amic acid, amic acid salt, esteracid, ester acid salt, diester, diamide, ester amide, and/or imidemoieties.

In one embodiment, the anhydride monomers may be functionalized by oneor more UV-absorbing compound(s) followed by polymerization to yieldUV-absorbing polymers. In an alternative embodiment, a polymer havingone or more reactive anhydride, ester acid, amic acid, ester acid salt,amic acid salt, diester, diamide, ester amide, and/or imide moieties onthe polymer backbone may be functionalized by post-polymerizationmodification reaction(s) to yield UV-absorbing polymers. The resultingUV-absorbing polymers include homopolymers, copolymers, terpolymers, andhigher homologues.

The polymer backbone may be a homopolymer of an anhydride monomer, suchas, poly(maleic anhydride), poly(dimethyl maleic anhydride), poly(methylmaleic anhydride), and poly(citaconic anhydride).

Alternatively, the polymer backbone may be provided by a copolymer. Onenon-limiting, exemplary member of this copolymer class may bepoly(styrene-co-maleic anhydride), which are a general class ofalternating copolymers of styrene and maleic anhydride, or thenon-equimolar copolymers containing less than about 50 mole percent ofthe anhydride monomer. This copolymer may be defined by its genericchemical structure:

wherein the subscripts y and z represent the molar ratios of therepeating units. The styrene constituent in poly(styrene-co-maleicanhydride) may be replaced in whole or in part by other vinylaromaticmonomers such as alpha-methylstyrene, nuclear methylstyrenes,ethylstyrene, iso-propylstyrene, tert-butylstyrene, chloro styrenes,dichlorostyrenes, bromostyrenes, dibromostyrenes, vinylnaphthalene andthe like. Similarly, the maleic anhydride can be replaced in whole or inpart by another alpha, beta-unsaturated cyclic dicarboxylic acidanhydride such as citraconic, chloromaleic, itaconic, bromomaleic,dichloromaleic, dibromomaleic, phenylmaleic, and the like. Particularly,the alpha, beta-unsaturated cyclic anhydride may be maleic anhydride.Suitable poly(styrene-co-maleic anhydride) copolymers may be prepared byany of the several methods available for the preparation ofstyrene-maleic anhydride copolymers or they may be purchasedcommercially. Non-equimolar copolymers may be prepared by solutionpolymerization directly from the respective monomers by the incrementaladdition of the reactive monomer as taught by U.S. Pat. No. 2,971,939,by a continuous recycle polymerization process such as described in U.S.Pat. Nos. 2,769,804 and 2,989,517, by the suspension polymerizationprocess described in U.S. Pat. No. 3,509,110, or by numerous knownvariations.

A second non-limiting example of a copolymer is a poly(alkyl vinylether-co-anhydride), such as poly(methyl vinyl ether-co-maleicanhydride):

wherein the subscripts y and z represent the molar ratios of therepeating units.

Particularly, this copolymer may be predominantly alternatingpoly(methyl vinyl ether-co-maleic anhydride).

Poly(methyl vinyl ether-co-maleic anhydride) is offered for commercialsale as Gantrez™ AN by International Specialty Products (Wayne, N.J.).

Regardless of the synthesis approach, the imide forms can be createdfrom the amic acid form through the application of heat, the use of areaction catalyst, or the use of a reaction initiator, or combinationsthereof.

The polymers and UV-bound polymers described herein may have aweight-average molecular weight from about 800 Da to about 5,000,000 Da,more particularly from about 10,000 Da to about 1,000,000 Da, and yetmore particularly from about 20,000 Da to about 500,000 Da. Themolecular weight may be controlled using methods known in the art,including strategies to control the reaction temperature and time, aswell as the use of chain-transfer agents such as thiols (e.g., dodecylmercaptan), and halocarbons (e.g., chlorinated compounds like carbontetrachloride) families of compounds employed for such purposes.

In another aspect, the invention provides formulations comprising one ormore UV-absorbing polymers described herein.

The UV-absorbing polymers according to the invention may be used aloneor in combination with other ingredient(s) in various formulations andproduct forms. The amount of each ingredient in the composition variesdepending on the type of composition, the function and/orphysicochemical property of the ingredient, and the amount of otherco-ingredients. The precise amount of each ingredient may be easilydetermined by any person skilled in the related arts. Such formulationsinclude, but are not limited to personal care formulations, adhesives,coatings, paints, electronics, Household, Industrial and Institutional(HI&I) compositions, inks, paper, polish, printing, membranes, metalworking fluids, oilfield formulations, construction formulations,plastics and plasticizers, textiles, industrial formulations, printing,lubricants, biocides, preservative, pharmaceuticals, food, agrochemical,and wood-care formulations.

The term “personal care formulation” refers to a composition intendedfor use on or in the human body. Non-limiting, but specific types ofpersonal care formulations include hair care compositions (encompassingstyling and non-styling compositions), sun care compositions(encompassing after-sun compositions), skin care compositions, and oralcare compositions.

Non-limiting applications of the hair care compositions include: hairstyling, hair setting, hair sculpting, hair curling, hair holding, hairwaving, hair fixing, hair maintaining, hair shaping, hair straightening,hair volumizing, hair relaxing, shampooing, hair conditioning, haircleansing, promoting hair style durability, imparting humidityresistance to hair and hair styles, enhancing hair shine, repairingsplit ends of hair, enhancing hair manageability such as lightness,smoothness, softness, disentangling and/or suppleness of hair,modulating hair stylability, protecting hair from thermal damage, hairdyeing, hair coloring, hair bleaching, oxidation dyeing of hair,limiting hair color bleeding, protecting hair color, hair treating(e.g., anti-dandruff), anti-hair fall, and protecting hair from UVradiation.

The hair care compositions of the invention may be particularly used inhair styling. More particularly, the hair care compositions may be usedto improve the hair stiffness, curl retention, and/or hair conditioning.

In particular embodiments, the hair care compositions may comprise thepolymer(s) described herein in an amount from about 0.1% to about 50% byweight of the composition. More particularly, the polymer(s) may bepresent in an amount from about 0.5% to about 20% by weight, mostparticularly from about 1% to about 10% by weight of the composition.

The hair care compositions may further comprise one or more additionalingredients. Particularly, the additional ingredients may be selectedfrom the group consisting of: skin care or hair care agents, hairstyling agents, hair fixative agents, film formers, structurants,gelling agents, surfactants, thickeners, preservatives, viscositymodifiers, electrolytes, pH adjusting agents, perfumes, dyes,organosilicon compounds, anti-dandruff agents, anti-foaming agents,anti-frizz agents, penetrants, vitamins, conditioning agents, chelatingagents, antimicrobial agents, preservatives, UV absorbers, sunscreens,natural extracts, propellants, carriers, diluents, solvents,pharmaceutical actives, lubricants, combing aids, plasticizers,solubilizers, neutralizing agents, vapor pressure suppressants,bleaching agents, hydrating agents, moisturizers, cosmetic adjuvantsand/or additives, protectants, and mixtures thereof.

The formulations according to the invention may further comprise one ormore UV actives that is/are different from the UV-absorbing compoundsdescribed herein.

Non-limiting examples of such UV actives include2,4-bis-(2,4-dihydroxyphenyl)-6-(4-methoxyphenyl)-s-triazine,aminobenzoic acid; 2-aminobenzophenone; amyl dimethyl PABA;bemotrizinol; benzophenone-3; benzophenone-4; benzophenone-9;2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol;2-(2H-benzotriazole-2-yl)-4-methylphenol;2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol;bis-benzoxazoyl phenyl ethylhexyl amino triazine; 3-benzylidene camphorsulfonic acid; CAS number 152261-33-1;N,N′-bisformyl-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylendiamine;bisoctrizole;2-[(p-(tert-butylamido)-anilino]-4,6-bis[(p-(2′-ethylhexyl-1′-oxycarbonyl)-anilino]-1,3,5-triazine;6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol;2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol; camphorbenzalkonium methosulfate; diethanolamine p-methoxycinnamate;diethylaminohydroxybenzoylhexylbenzoate; diethylhexyl butamido triazone;digalloyl trioleate; dioxybenzone; disodium phenyl dibenzimidazoletetrasulfonate; drometrizole trisiloxane; ecamsule; ensulizole; ethyl4-bis(hydroxypropyl) aminobenzoate; ethylhexyl p-methoxycinnamate;2-ethylhexyl salicylate; ethylhexyl triazone;beta-2-glucopyranoxypropylhydroxybenzophenone; glyceryl aminobenzoate;homomenthyl salicylate; [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone;2-[bis(2-hydroxyethyl)amino]ethyl salicylate;(E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid; lawsone withdihydroxyacetone; meradimate; methoxycinnamido propyl hydroxy sultainementhyl anthranilate; meradimate; methyl-2-aminobenzoate; oxybenzone;2-phenylbenzimidazole-5-sulfonic acid (and its potassium, sodium andtriethanolamine salts); sulisobenzone;bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate; sterically hinderedoligomeric amine, triethanolamine salicylate, and combinations thereof.

Non-limiting applications of the sun care compositions include:protecting skin and/or hair from UV radiation (including any or all ofUV-A, UV-B and/or UV-C radiation), sun screening, skin anti-irritating,skin repairing, skin wrinkle masking, skin nourishing, skinmoisturizing, skin relaxing, skin refreshing, skin cooling, skinsoothing, skin tanning, skin tan prolonging, sun-less skin tanning, skinglowing, skin micro-glittering, skin shimmering, and skin anti-tanning.

Non-limiting applications of the skin care compositions include:protecting skin from UV radiation (including any or all of UV-A, UV-Band/or UV-C radiation), skin cleansing, face cleansing, body cleansing,insect repelling, antiperspirant, exfoliating skin, rejuvenating skin,influencing cell turnover, deodorant, astringent, imparting waterresistance or water proofness to skin, decreasing and/or minimizing theappearance of skin wrinkles, decreasing and/or minimizing the appearanceof skin blemishes (such as lentigo, skin discolorations, pimples, and/oracne), changing skin color (including skin lightening, skin brightening,skin color darkening, and color cosmetics for the face, cheeks, lips,eyelids, and/or eye lashes), skin iridescing, skin glossing, curling ofeye lashes, eye lining, eye shadowing, mascara, removing facial and/orbody hair, skin tightening, skin tanning, skin bronzing, skin blushing,prolonging skin tan, sun-less skin tanning, anti-tanning, skinanti-bacterial, skin anti-oxidant, skin anti-photoaging, skinanti-seborrheic, cell exchange and/or cell respiration activating ofskin, skin conditioning, skin detoxifying, skin emollient, skinmoisturizing, film forming on skin, skin healing-cicatrizing, skinimmune-protecting, skin plumping, glossing, shading, plumping, and/orcoloring of lips, skin revitalizing, skin energizing, skin re-sculpting,skin nourishing, skin smoothing, skin slimming, skin anti-irritating,and skin sanitizing.

Non-limiting applications of the oral care compositions include: toothand/or mouth cleansing, providing denture adhesion, delivering and/orretaining actives to oral cavity, mouth washing, mouth refreshing, mouthrinsing, mouth gargling, providing oral hygiene, preventing, reducing,controlling, and/or removing tooth stain, preventing and/or controllingtooth decay, preventing and/or controlling tartar, tooth flossing, toothwhitening and/or bleaching, mouth treating, and tooth filling.

The polymers described herein also may be used alone or in combinationwith other ingredient(s) in pharmaceutical and/or nutritionalcompositions.

Non-limiting applications of the pharmaceutical and/or nutritionalcompositions include: providing anti-tack, binder, coating,disintegrating, dispersing, encapsulating, filling, film forming,lubricating, and solubilizing. Additional insight into how the polymersdescribed herein find application in this art area may be found in thefollowing publications by Ashland Specialty Ingredients: Health andnutrition product guide—Performance enhancing products (August 2008),Plasdone™ povidones product overview (April 2010), Plasdone™ K-12 andK-17 povidones—Solubilizers for liquid softgel fill formulations(September 2010), Plasdone™ K-29/32 povidone—High efficiency binder forwet granulation (April 2010), Plasdone™ S-630 copovidone—ProductOverview (April 2010), Polyplasdone™ Ultra and Ultra-10crospovidones—Product overview (September 2010), Polyplasdone™superdisintegrants—Product overview (July 2010), Polyplasdone™crospovidone—Superdisintegrants for orally disintegrating and chewabletablets (July 2010), Polyplasdone™ crospovidone—Nonionicsuperdisintegrant for improved dissolution of cationic drugs (July2009), Polyplasdone™ crospovidone—The solution for poorly soluble drugs(July 2009), Polyplasdone™ crospovidone—Novel pelletization aid forextrusion spheronization (July 2010), PVP-Iodine povidone iodineantiseptic agent (March 2004), and Pharmaceutical technicalbulletin—PVP-Iodine for prophylaxis and treatment of bovine mastitis(December 2003). Each publication is hereby incorporated in its entiretyby reference.

Any range in composition pH may be used. In embodiments wherein thecomposition may be applied to keratinous material, the pH may range fromabout 2 to 12. pH may be adjusted to a desired value by means of addingone or more acidifying or alkalinizing agents that are well-known in thestate of the art. For example, the composition can contain at least onealkalizing or acidifying agent in amounts from about 0.01% to about 30%based on the total weight of the composition.

Non-limiting examples of acidifying or acidic pH adjusting agentsinclude organic acids, such as citric acid, acetic acid, carboxylicacids, α-hydroxyacids, β-hydroxyacids, α,β-hydroxyacids, -hydroxyacids,salicylic acid, tartaric acid, lactic acid, glycolic acid, natural fruitacids, and combinations thereof. In addition, inorganic acids, forexample hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid,phosphoric acid, and combinations thereof can be utilized.

Non-limiting examples of alkalizing or alkaline pH adjusting agentsinclude ammonia, alkali metal hydroxides (such as sodium hydroxide andpotassium hydroxide), ammonium hydroxide, alkanolamines (such as mono-,di- and triethanolamine), diisopropylamine, dodecylamine,diisopropanolamine, aminomethyl propanol, cocamine, oleamine,morpholine, triamylamine, triethylamine, tromethamine(2-amino-2-hydroxymethyl)-1,3-propanediol), andtetrakis(hydroxypropyl)ethylenediamine, hydroxyalkylamines andethoxylated and/or propoxylated ethylenediamines, alkali metal salts ofinorganic acids, such as sodium borate (borax), sodium phosphate, sodiumpyrophosphate, and the like, and mixtures thereof.

Non-limiting examples of alkalizing agent can be chosen from ammonia,alkali carbonates, alkanolamines, like mono-, di- and triethanolamines,as well as their derivatives, sodium or potassium hydroxides andcompounds of the following formula:

wherein R₁ may be a propylene residue that may be optionally substitutedwith an hydroxyl group or a C1-C4 alkyl radical; R₂, R₃, R₄ and R₅ areidentical or different and represent a hydrogen atom, a C1-C4 alkylradical or C1-C4 hydroxyalkyl radical.

The composition also may comprise one or more buffers. Suitablebuffering agents include but are not limited to alkali or alkali earthcarbonates, phosphates, bicarbonates, citrates, borates, acetates, acidanhydrides, succinates and the like, such as sodium phosphate, citrate,borate, acetate, bicarbonate, and carbonate. The personal carecompositions may be formulated in any of the product forms known to aperson of ordinary skill in the art. Non-limiting product forms aredescribed below.

Product Forms

Non-limiting hair care product forms include: shampoos, conditioners,aerosols, mousses, sprays, mists, gels, waxes, creams, lotions, glues,pomades, spritzes, solutions, oils, liquids, solids, W/O emulsions, O/Wemulsions, suspensions, multiple emulsions, microemulsions,microencapsulated products, sticks, balms, tonics, pastes,reconstitutable products, nanoemulsions, solid lipid nanoparticles,liposomes, cubosomes, neosomes, putties, lacquers, serums, perms,volumizers, packs, flakes, 2-in-1 shampoo/conditioner products, and3-in-1 shampoo/conditioner/styling products.

The compositions according to the invention may also take the form ofafter-shampoo compositions, to be rinsed off or not, for permanents,straightening, waving, dyeing, or bleaching, or the form of rinsecompositions to be applied before or after dyeing, bleaching,permanents, straightening, relaxing, waving or even between the twostages of a permanent or straightening process.

Non-limiting sun care product forms include: solutions, liquids, creams,powders, lotions, gels, pastes, waxes, aerosols, sprays, mists,roll-ons, sticks, milks, emulsions, and wipes.

Non-limiting skin care product forms include: solutions, oils, lotions,creams, ointments, liquids, gels, solids, W/O emulsions, O/W emulsions,milks, suspensions, microemulsions, dispersions, microencapsulatedproducts, sticks, balms, tonics, pastes, mists, reconstitutableproducts, peels, soaps, aerosols, mousses, waxes, glues, pomades,spritzes, putties, lacquers, serums, perms, powders, pencils, flakes,blush, highlighters, bronzers, concealers, and 2-way cake products.

The compositions of the invention may also take the form of skin-washingcompositions, and particularly in the form of solutions or gels for thebath or shower, or of make-up removal products.

The six skin care product categories that follow next may be considereda subset of the skin and sun care products:

(1) Eye Care

Non-limiting eye care product forms include: mascaras, eye liners, eyeshadows, curlers of eye lashes, eyebrow pencils, and eye pencils.

(2) Lip Care

Non-limiting lip care product forms include: lipsticks, lip balms, lippencils, lip glosses, lip sprays, transparent lip bases, tinted lipmoisturizers, and multi-functional color sticks that can also be usedfor cheeks and eyes.

(3) Nail Care

Non-limiting nail care product forms include: nail polishes, nailvarnishes, enamels, nail varnish removers, home-manicure products suchas cuticle softeners and nail strengtheners, and artificial nails.

(4) Face Care

Non-limiting face care product forms include: creams, lotions,solutions, oils, liquids, peels, scrubs, emulsions, suspensions,microemulsions, microencapsulated product, pastes, reconstitutableproduct, aerosols, mousses, gels, waxes, glues, pomades, spritzes,facial wet-wipes, putties, lacquers, serums, perms, powders, blush,highlighters, bronzers, masks, and concealers.

(5) Body Care

Non-limiting body care product forms include: foams, peels, masks, gels,sticks, aerosols, lotions, salts, oils, balls, liquids, powders, peels,pearls, bar soaps, liquid soaps, body washes, cleansers, scrubs, creams,flakes, other bath and shower products, shaving products, waxingproducts, and sanitizers.

(6) Foot Care

Non-limiting foot care product forms include: mousses, creams, lotions,powders, liquids, sprays, aerosols, gels, flakes, and scrubs.

Non-limiting oral care product forms include: toothpastes, adhesives,gums, gels, powders, creams, solutions, lotions, liquids, dispersions,suspensions, emulsions, tablets, capsules, rinses, flosses, aerosols,strips, films, pads, bandages, microencapsulated products, syrups, andlozenges.

Also contemplated are personal care compositions comprising polymer(s)described herein complexed with iodine. These compositions may be usedin treating skin conditions, non-limiting examples of which includedermatitis, wounds, bacterial infections, burns, rashes, and herpes.These complexed compositions may be staining, substantiallynon-staining, or essentially non-staining.

Examples of related personal care compositions are disclosed in U.S.Pat. Nos. 5,599,800; 5,650,166; 5,916,549; and 6,812,192; U.S. patentapplication 2009/0317432; EP 556,660; 661,037; 661,038; 662,315;676,194; 796,077; 970,682; 976383; 1,415,654; and 2,067,467; and WO2005/032506; each of which is hereby incorporated in its entirety byreference.

It is also contemplated that the personal care compositions may be usedin products for male and/or female personal grooming and/or toiletrysuch as: sanitary napkins, baby diapers, adult diapers, feminineproducts, products for incontinence, and other related products.

An array of additional personal care compositions, methods, and uses arecontemplated. Disclosure of these compositions may be found in thefollowing brochures by Ashland Specialty Ingredients, each of which ishereby incorporated in its entirety by reference: Plasdone® K-29/32,Advanced non-oxidative, non-abrasive teeth whitening in toothpastes,mouthwashes, and oral rinses (2010), Polymers for oral care, product andapplications guide (2002), A formulation guide for excellent hairstyling gels and lotions (April 2003), PVP (polyvinylpyrrolidone) (nodate provided), and Textile chemicals, solutions for the mostchallenging product environment (no date provided).

Also contemplated are additional personal care compositions that maycomprise the polymers described herein. Disclosures on such compositionsmay be found in the publications listed below, each of which is herebyincorporated in its entirety by reference: (1) PrototypeFormulations—Personal Care Products (2009) from Xiameter, Dow Corning.(2) Sun care formulations under the category “Refreshing Sun”, “YoungerSun”, “Sun for Men”, and “Sunny Glow” from Dow Corning. (3) CosmeticNanotechnology, Polymers and Colloids in Cosmetics, 2007, ACS SymposiumSeries. (4) Review Paper: Lipid nanoparticles (SLN, NLC) in cosmetic andpharmaceutical dermal products, International Journal of Pharmaceutics,Volume 366, 2009.

Optional: Additional Composition Ingredients

It is also contemplated that the personal care compositions optionallymay contain one or more additional ingredients.

Further, it is contemplated that the composition ingredients may beformulated in a single container, or the ingredients may be formulatedin-part in two or more distinct containers of the same or differenttype, the contents of which may require mixing prior to use.

Furthermore, it also is contemplated that the compositions may beprepared in the form of concentrates that may be diluted by a suitablesubstance(s) prior to use. The concentrate may, in turn, be present inany of the forms as described under ‘Product Forms’ for the personalcare compositions of the invention.

A non-limiting list of classes of additional ingredients that mayoptionally be present in different types of personal care compositionsis provided below: conditioning agents, antimicrobials, protectives (forexample, antiradical agents), abrasives, UV absorbers, emulsifiers(including, but not limited to ethoxylated fatty acids, ethoxylatedglyceryl esters, ethoxylated oils, ethoxylated sorbitan esters, fattyesters, PEG esters, polyglycerol esters), antiperspirants (including,but not limited to aluminium chlorohydrates, aluminium zirconiumchlorhydrates), antioxidants, vitamins and/or provitamins, botanicals,fixatives, oxidizing agents, reducing agents, dyes, cleansing agents,anionic, cationic, nonionic, and/or amphoteric surfactants, thickenersand/or gelling agents, perfumes, flavors, and/or fragrances, pearlizingagents, stabilizers, pH adjusters, filters, antimicrobial agents,preservatives and/or disinfectants, associative polymers, oils ofvegetable, mineral, and/or synthetic origin, polyols, silicones,colorants, bleaching agents, highlighting agents, propellants(including, but not limited to hydrocarbons, dimethyl ether,fluorocarbons), styling polymers, benefit agents, skin tighteners(including, but not limited to arbutin and kojic acids), tanning agents(including, but not limited to dihydroxyacetone), solvents and/orcosolvents, diluents, essential oils, sequestrants and/or chelators,carriers, and natural extracts and/or natural products.

The amount of each ingredient in the composition varies depending on thetype of composition, the function and/or physicochemical property of theingredient, and the amount of other co-ingredients. The precise amountof each ingredient may be easily determined by any person skilled in therelated arts.

It may be desirable to include one or more ingredients described in theprior art disclosures IPCOM000186541D, IPCOM000128968D, andIPCOM000109682D on www.ip.com, the contents of each of these disclosuresare hereby incorporated in their entirety by reference.

Further reference to formulary co-ingredients and product forms includethe disclosures in US 2010/0183532, paragraphs [0096]-[0162], and WO2010/105050, paragraphs [0053]-[0069], the contents of which are herebyincorporated in their entirety by reference.

Non-limiting examples of structurants that may be used in the hair carecompositions according to the invention include dextrin palmitate,trihydroxystearin, hydroxy stearic acid, hydrophilic or hydrophobicsilica, hydrophobically modified clay selected from the group consistingof stearalkonium hectorite, quaternium-18 bentonite, quaternium-18hectorite, disteardimonium hectorite, derivatives thereof, and mixturesthereof.

The hair care compositions of the invention may additionally compriseone or more hair styling agents, hair fixative agents, and/or filmformers.

Particularly useful as styling agents are hair styling polymers. Thehair styling polymers may be cationic, anionic, amphoteric or nonionicin nature. The polymers may be synthetic or naturally derived.Non-limiting examples of hair styling polymers include the followingpolymer products available for sale from Ashland Specialty Ingredients:(1) Cationic styling polymers with hair conditioning benefits—Styleze™ WPolymer, Styleze™ CC-10 (pseudo cationic), Gafquat™ 755 NP, and Gafquat™440; (2) Styling polymers with excellent high humidity curlretention—Styleze™ 2000, Allianz™ LT 120, Styleze™ W Polymer, andAdvantage™ LCA; (3) Non-ionic styling polymers with broad ingredientcompatibility—Polyvinylpyrrolidones such as PVP K-30, PVP K-60 and PVPK-90, Vinylpyrrolidone/vinyl acetate copolymers such as PVP/VA (E, I orW) 735, PVP/VA (E or W) 635, PVP/VA (E or I) 535, PVP/VA (E or I) 335and PVP/VA S-630, andpoly(vinylpyrrolidone/dimethylaminoethylmethacrylate) polymers such asCopolymer 845/937. Additional details on the aforementioned polymers andmethods of use, or formulations thereof, may be found in a publicationfrom Ashland Specialty Ingredients titled “A Formulation Guide forExcellent Hair Styling Gels and Lotions” (2002) that is herebyincorporated in its entirety by reference.

A non-limiting example of hair fixative agent that may be used in haircare compositions according to the invention includes a hair fixativepolymer available for sale from Ashland Specialty Ingredients,AquaStyle™ 300 (INCI name Polyquaternium-69). A related publication fromAshland Specialty Ingredients titled “Aquastyle® 300, A Fixative Polymerwith Enhanced Styling Benefits” (2007) is hereby incorporated in itsentirety by reference.

Non-limiting examples of film formers that may be used in hair carecompositions according to the invention include film forming polymersavailable for sale from Ashland Specialty Ingredients such as (1)Aquaflex™ FX 64, (2) AquaCat™ clear cationic solution, (3) Aqualon™carboxymethylcellulose, (4) Klucel™ hydroxypropylcellulose, and (5)Primaflo™ HP22 polymer solution.

Further details on hair styling agents, hair fixative agents, and/orfilm formers may be found in U.S. Pat. Nos. 7,871,600, 7,205,271,7,122,175, 7,041,281, 6,998,114, 6,749,836, 6,689,346, 6,599,999,6,562,325, 6,413,505, 6,387,351, 6,228,352, 5,643,581, 5,922,312,5,897,870, 5,879,669, 5,709,850, 5,753,216 and 5,632,977 each of whichis hereby incorporated in its entirety by reference.

Non-limiting examples of anti-frizz agents that may be used in hair carecompositions according to the invention include anti-frizz polymersavailable for sale from Ashland Specialty Ingredients such as AquaStyle™300 and Styleze™ XT3. Information on related anti-frizz agents may befound in U.S. Pat. Nos. 7,914,773, 7,785,575, and U.S. publishedapplication 2010/00093584, the disclosures of each of which is herebyincorporated in its entirety by reference.

One or more plasticizers or coalescing agents may be added to modify thefilm forming characteristics of hair care compositions according to theinvention. Non-limiting examples of plasticizers include glycols, adipicesters, phthalate esters, isobutyrate esters, terephthalate esters,epoxidized butyl esters or fatty acids, epoxidized vegetable oils,glycerine, di-2-ethylhexyladipate or dioctyladipate (DOA),di-2-ethylhexyl phthalate or dioctyl phthalate (DOP), di-2-ethylhexylterephthalate (DOTP), dicyclohexyl phthalate, diisononyl adipate,diisononylphthalate, n-butyl benzyl phthalate, 1,3-butyleneglycol/adipic acid polyester, dialkyl adipate, dialkyl phthalatederivatives where the alkyl group is a C₁-C₁₂ alkyl group,di-n-hexylazelate, diphenylphthalate, tricresol phosphate, benzylbenzoate, dibutyl phosphate, tributyl phosphate, tributoxyethylphosphate, triphenyl phosphate, butyl acetyl ricinoleate, glycerolacetyl ricinoleate, dibutyl phthalate, diethyl phthalate, dioctylphthalate, dimethoxyethyl phthalate, diisobutyl phthalate, diamylphthalate, dibutyl glycolate, butyl stearate, triethyl citrate, tributylcitrate, tributyl acetyl citrate, 2-hexyltriethylacetyl citrate, dibutyltartarate, camphor, epoxidized butyl esters of linseed oil fatty acids,epoxidized linseed oil, epoxidized soya oil, propylene glycol adipate,2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), methyl abietate,cumyl acetate, dibutoxyethyl adipate, di-n-hexylazalate,glyceryl-tri-benzerate, tri-n-butylcitrate, dioctyl fumarate, triisonyltrimellitate, dioctyl isophthalate, butyl oleate, chlorinated paraffin,tricresolphosphate, dibutyl sebacate, dimethicone copolyol (Dow Corning190), PEG-6 capric/caprylic glyceride (SOFTIGEN 767), DIACETIN,LAURAMIDE DEA (MONAMID 716), phenyl trimethicone (ABIL AV 20-1000),propylene glycol, dipropylene glycol, as well as polymeric plasticizers,and mixtures thereof. Non-limiting examples of coalescing solventsinclude acetone, methyl acetate, and di- or tri-propylene glycol methylethers, and mixtures thereof. Further examples of plasticizers may befound in U.S. Pat. Nos. 5,753,216 and 5,676,935, the disclosures of eachof which are hereby incorporated in its entirety by reference.

Non-limiting examples of propellants that may be used in hair carecompositions of the invention include trichlorofluoromethane,chlorodifluoromethane, 1,1-difluoroethane, dichlorotetrafluoroethane,monochlorodifluoromethane, trichlorotrifluoroethane, dimethyl ether,C₁-C₄ hydrocarbons such as methane, ethane, propane, n-butane, andisobutane, water-soluble gases such as, dimethyl ether, carbon dioxide,and/or nitrous oxide, and insoluble, compressed gases such as nitrogen,helium, and fully-fluorinated oxetanes and oxepanes, and mixturesthereof.

Non-limiting examples of penetrants that may be used in hair carecompositions of the invention include lanolin compounds, proteinhydrolysates, protein derivatives, and mixtures thereof.

Non-limiting examples of anti-foaming agents that may be used in haircare compositions of the invention include carrier oils, silicone oils,silicone foam inhibitors, hydrophobic silica, hydrophobic fatderivatives, waxes, water-insoluble polymers, amphiphilic components,emulsifiers, coupling agents, and mixtures thereof.

Any known conditioning agent may be used in the personal carecompositions of the invention. An extensive discussion on conditioningagents may be found in the book Conditioning Agents for Skin and Hair,Cosmetic Science and Technology Series, Volume 21, 1999, Marcel DekkerPublishers. The contents of the book are hereby incorporated in itsentirety by reference.

Conditioning agents may be chosen from synthetic oils, mineral oils,vegetable oils, fluorinated or perfluorinated oils, natural or syntheticwaxes, silicones, cationic polymers, proteins and hydrolyzed proteins,cationic surfactants, ceramide type compounds, fatty amines, fatty acidsand their derivatives, as well as mixtures of these different types ofcompounds.

Non-limiting examples of suitable synthetic oils include: polyolefins,e.g., poly-α-olefins, such as polybutenes, polyisobutenes, polydecenes,and blends thereof. The polyolefins may be hydrogenated.

Non-limiting examples of suitable mineral oils include hexadecane andoil of paraffin.

Non-limiting examples of suitable animal and vegetable oils include:sunflower oil, corn oil, soy oil, avocado oil, jojoba oil, squash oil,raisin seed oil, sesame seed oil, walnut oil, fish oil, glyceroltricaprocaprylate, purcellin oil, liquid jojoba, and blends thereof.Also suitable are natural oils such as oils of eucalyptus, lavender,vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory,nutmeg, cinnamon, hyssop, caraway, orange, geranium, cade, bergamot, andblends thereof.

The conditioning agent may be a fluorinated or a perfluorinated oil. Thefluoridated oils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons such asperfluorodecahydronaphthalene, fluoroesters, fluoroethers, and blendsthereof.

Non-limiting examples of suitable natural and synthetic waxes include:carnauba wax, candelila wax, alfa wax, paraffin wax, ozokerite wax,vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax,absolute flower waxes such as black currant flower wax, animal waxessuch as bees wax, modified bees wax (cerabellina), marine waxes andpolyolefin waxes such as polyethylene wax, and blends thereof.

The conditioning agent may be any silicone known by those skilled in theart. Silicones include polyorganosiloxanes that are insoluble in thecomposition. The silicones may be present in the form of oils, waxes,resins, or gums. They may be volatile or non-volatile.

Non-limiting examples of suitable silicones include: polyalkylsiloxanes, polyaryl siloxanes, polyalkyl aryl siloxanes, silicone gumsand resins, polyorgano siloxanes modified by organofunctional groups,and blends thereof.

Suitable polyalkyl siloxanes include polydimethyl siloxanes withterminal trimethyl silyl groups or terminal dimethyl silanol groups(dimethiconol) and polyalkyl (C1-C20) siloxanes. Suitable polyalkyl arylsiloxanes include polydimethyl methyl phenyl siloxanes and polydimethyldiphenyl siloxanes. The siloxanes can have a linear or branchedstructure.

Suitable silicone gums include polydiorganosiloxanes, such as thosehaving a number-average molecular weight between 200,000 Da and1,000,000 Da used alone or mixed with a solvent.

Non-limiting examples of suitable silicone gums include: polymethylsiloxane, polydimethyl siloxane/methyl vinyl siloxane gums, polydimethylsiloxane/diphenyl siloxane, polydimethyl siloxane/phenyl methylsiloxane, polydimethyl siloxane/diphenyl siloxane/methyl vinyl siloxane,and blends thereof.

Non-limiting examples of suitable silicone resins include silicones witha dimethyl/trimethyl siloxane structure and resins of the trimethylsiloxysilicate type.

The organo-modified silicones suitable for use in the invention includesilicones such as those previously defined and containing one or moreorganofunctional groups attached by means of a hydrocarbon radical, andgrafted silicone polymers. The organo-modified silicones may be one fromthe amino functional silicone family.

The silicones may be used in the form of emulsions, nano-emulsions, ormicroemulsions.

The cationic polymers that may be used as conditioning agents accordingto the invention generally have a molecular weight (average number) fromabout 500 Da to about 5,000,000 Da, and particularly from about 1,000 Dato about 3,000,000 Da. The expression “cationic polymer” as used hereinindicates any polymer having at least one cationic group.

The cationic polymers may be chosen from among polymers containingprimary, secondary, tertiary amine, and/or quaternary ammonium groupsthat may form part of the main polymer backbone and/or side chain(s).

Non-limiting examples of suitable cationic polymers include polyamines,polyaminoamides, and quaternary polyammonium classes of polymers, suchas:

(1) homopolymers and copolymers derived from acrylic or methacrylicesters or amides. The copolymers may contain one or more units derivedfrom acrylamides, methacrylamides, diacetone acrylamides, acrylic ormethacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinyl caprolactam, and vinyl esters. Non-limiting,specific examples include: copolymers of acrylamide and dimethyl aminoethyl methacrylate quaternized with dimethyl sulfate or with an alkylhalide; copolymers of acrylamide and methacryloyl oxyethyl trimethylammonium chloride; the copolymer of acrylamide and methacryloyl oxyethyltrimethyl ammonium methosulfate; copolymers of vinyl pyrrolidone anddialkylaminoalkyl acrylate or methacrylate, optionally quaternized, suchas the products sold under the name Gafquat™ by Ashland SpecialtyIngredients; terpolymers of dimethyl amino ethyl methacrylate, vinylcaprolactam, and vinyl pyrrolidone such as the product sold under thename Gaffix™ VC 713 by Ashland Specialty Ingredients; the vinylpyrrolidone/methacrylamidopropyl dimethylamine copolymer, marketed underthe name Styleze™ CC 10 by Ashland Specialty Ingredients; and the vinylpyrrolidone/quaternized dimethyl amino propyl methacrylamide copolymerssuch as the product sold under the name Gafquat™ HS 100 by AshlandSpecialty Ingredients (Wayne, N.J.).

(2) derivatives of cellulose ethers containing quaternary ammoniumgroups, such as hydroxy ethyl cellulose quaternary ammonium that hasreacted with an epoxide substituted by a trimethyl ammonium group.

(3) derivatives of cationic cellulose such as cellulose copolymers orderivatives of cellulose grafted with a hydrosoluble quaternary ammoniummonomer, as described in U.S. Pat. No. 4,131,576, such as hydroxy alkylcellulose, and hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulosegrafted with a salt of methacryloyl ethyl trimethyl ammonium,methacrylamidopropyl trimethyl ammonium, or dimethyl diallyl ammonium.

(4) cationic polysaccharides such as described in U.S. Pat. Nos.3,589,578 and 4,031,307, guar gums containing cationic trialkyl ammoniumgroups, and guar gums modified by a salt, e.g., chloride of 2,3-epoxypropyl trimethyl ammonium.

(5) polymers composed of piperazinyl units and alkylene or hydroxyalkylene divalent radicals with straight or branched chains, possiblyinterrupted by atoms of oxygen, sulfur, nitrogen, or by aromatic orheterocyclic cycles, as well as the products of the oxidation and/orquaternization of such polymers.

(6) water-soluble polyamino amides prepared by polycondensation of anacid compound with a polyamine. These polyamino amides may bereticulated.

(7) derivatives of polyamino amides resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids followed by alkylationby bi-functional agents.

(8) polymers obtained by reaction of a polyalkylene polyamine containingtwo primary amine groups and at least one secondary amine group with adioxycarboxylic acid chosen from among diglycolic acid and saturateddicarboxylic aliphatic acids having 3 to 8 atoms of carbon. Suchpolymers include those described in U.S. Pat. Nos. 3,227,615 and2,961,347.

(9) cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammoniumsuch as the homopolymer of dimethyl diallyl ammonium chloride andcopolymers of diallyl dimethyl ammonium chloride and acrylamide.

(10) quaternary diammonium polymers such as hexadimethrine chloride.

(11) quaternary polyammonium polymers, including, for example, Mirapol®A 15, Mirapol® AD1, Mirapol® AZ1, and Mirapol® 175 products sold byMiranol.

(12) quaternary polymers of vinyl pyrrolidone and vinyl imidazole suchas the products sold under the names Luviquat® FC 905, FC 550, and FC370 by BASF Corporation.

(13) quaternary polyamines.

(14) reticulated polymers known in the art.

Other cationic polymers that may be used include cationic proteins orhydrolyzed cationic proteins, polyalkyleneimines such aspolyethyleneimines, polymers containing vinyl pyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrins,quaternary polyurethanes, and derivatives of chitin.

The conditioning agent may comprise a protein or hydrolyzed cationic ornon-cationic protein. Non-limiting examples of suitable compoundsinclude: hydrolyzed collagens having triethyl ammonium groups,hydrolyzed collagens having trimethyl ammonium and trimethyl stearylammonium chloride groups, hydrolyzed animal proteins having trimethylbenzyl ammonium groups (benzyltrimonium hydrolyzed animal protein),hydrolyzed proteins having groups of quaternary ammonium on thepolypeptide chain, including at least one C1-C18 alkyl, and blendsthereof.

Non-limiting examples of suitable hydrolyzed cationic proteins include:Croquat® L, in which the quaternary ammonium groups include a C12 alkylgroup, Croquat® M, in which the quaternary ammonium groups includeC10-C18 alkyl groups, Croquat® S in which the quaternary ammonium groupsinclude a C18 alkyl group, Crotein® Q in which the quaternary ammoniumgroups include at least one C1-C18 alkyl group, and blends thereof.These products are sold by Croda.

The conditioning agent may also comprise quaternized vegetableprotein(s) such as wheat, corn, or soy proteins, non-limiting examplesof which include: cocodimonium hydrolyzed wheat protein, laurdimoniumhydrolyzed wheat protein, steardimonium hydrolyzed wheat protein,2-N-stearoyl amino-octadecane-1,3-diol, 2-N-behenoylamino-octadecane-1,3-diol,2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1,3-diol, 2-N-stearoylamino-octadecane-1,3,4-triol, n-stearoyl phytosphingosine, 2-N-palmitoylamino-hexadecane-1,3-diol, bis-(N-hydroxy ethyl n-cetyl) malonamide,n-(2-hydroxy ethyl)-N-(3-cetoxyl-2-hydroxy propyl) amide of cetylicacid, n-docosanoyl n-methyl-D-glucamine, and blends thereof.

The conditioning agent may also comprise a cationic surfactant such as asalt of a primary, secondary, or tertiary fatty amine, optionallypolyoxyalkylenated, a quaternary ammonium salt, a derivative ofimidazoline, or an amine oxide. Conditioning agents may also be selectedfrom the group consisting of: mono-, di-, and tri-alkyl amines, andquaternary ammonium compounds with a counterion such as a chloride, amethosulfate, a tosylate, etc. Non-limiting examples of suitable aminesinclude: cetrimonium chloride, dicetyldimonium chloride, behentrimoniummethosulfate, and blends thereof.

The conditioning agent may comprise a fatty amine. Non-limiting examplesof suitable fatty amines include: dodecyl amines, cetyl amines, stearylamines such as stearamidopropyl dimethylamine, and blends thereof.

The conditioning agent may comprise a fatty acid or derivative(s)thereof. Non-limiting examples of suitable fatty acids include: myristicacid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleicacid, isostearic acid, and blends thereof. The derivatives of fattyacids include carboxylic ester acids including mono-, di-, tri- andtetra-carboxylic acids esters, amides, anhydrides, esteramides, imides,and mixtures of these functional groups.

Also suitable as conditioning agents are the following commercialproducts:

(1) Aquacat™ Clear Cationic Solution (INCI Name: guarhydroxypropyltrimonium Chloride), n-Hance™ SP-100 (INCI Name:acrylamidopropyl trimonium chloride/acrylamide copolymer), and n-Hance™cationic guar (INCI Name: guar hydroxypropyltrimonium chloride) fromAshland Specialty Ingredients

(2) Salcare® from BASF Corp.

(3) Softcat™ Polymers from The Dow Chemical Company.

(4) Jaguar® C500, Polycare® Boost, Mackconditioner™ Brite, and Mackin®301 from Rhodia.

(5) Stepanquat® ML, Stepanquat® GA-90, Ninol®, and Ammonyx® from StepanCompany.

(6) Conditioneze™ 7 and Conditioneze™ NT-20 from Ashland SpecialtyIngredients (Wayne, N.J.).

Of course, mixtures of two or more conditioning agents may be used.

The conditioning agent(s) may be present in an amount from about 0.001%to about 20%, particularly from about 0.01% to about 10%, and even moreparticularly from about 0.1% to about 3% by weight of the composition.

Personal care compositions may optionally comprise antimicrobialagent(s).

Non-limiting examples of suitable water insoluble, non-cationicantimicrobial agents include: halogenated diphenyl ethers, phenoliccompounds including phenol and its homologs, mono and poly-alkyl andaromatic halophenols, resorcinol and its derivatives, bisphenoliccompounds and halogenated salicylanilides, benzoic esters, halogenatedcarbanilides, and blends thereof.

Non-limiting examples of suitable water soluble antimicrobial agentsinclude: quaternary ammonium salts, bis-biquanide salts, triclosanmonophosphate, and blends thereof.

The quaternary ammonium agents include those in which one or two of thesubstituents on the quaternary nitrogen has a carbon chain length(typically alkyl group) from about 8 to about 20, typically from about10 to about 18 carbon atoms, while the remaining substituents (typicallyalkyl or benzyl group) have a lower number of carbon atoms, such as fromabout 1 to about 7 carbon atoms, typically methyl or ethyl groups.

Non-limiting examples of suitable quaternary ammonium antibacterialagents include: Dodecyl trimethyl ammonium bromide, tetradecylpyridiniumchloride, domiphen bromide, n-tetradecyl-4-ethyl pyridinium chloride,dodecyl dimethyl(2-phenoxyethyl)ammonium bromide, benzyl dimethylstearylammonium chloride, cetyl pyridinium chloride, quaternized5-amino-1,3-bis(2-ethyl-hexyl)-5-methyl hexahydropyrimidine,benzalkonium chloride, benzethonium chloride, methyl benzethoniumchloride, and blends thereof.

Other antimicrobial compounds are bis[4-(R-amino)-1-pyridinium]alkanesas disclosed in U.S. Pat. No. 4,206,215. Other antimicrobials such ascopper salts, zinc salts and/or stannous salts may also be included.Also useful are enzymes, including endoglycosidase, papain, dextranase,mutanase, and blends thereof. Such antimicrobial agents are disclosed inU.S. Pat. Nos. 2,946,725 and 4,051,234. The antimicrobial agents mayalso comprise chlorhexidine, triclosan, and flavor oils such as thymol.Triclosan and other agents are disclosed in U.S. Pat. Nos. 5,015,466 and4,894,220.

In particular embodiments, one or more preservatives may be included.

Non-limiting examples of suitable preservatives include: benzoic acid,sorbic acid, dehydroacetic acid, diazolidinyl ureas, imidazolidinylureas, salicylic acid, piroctone olamine, DMDM hydantoin, IPBC(iodopropynyl butylcarbamate), triclosan, bronopol, formaldehyde,isothiazolinones, nitrates/nitrites, parabens, phenoxyethanol, potassiumsorbate, sodium benzoate, sulphites, sulphur dioxide, and blendsthereof.

In particular embodiments, preservative boosters/solvents may beincorporated, non-limiting examples of which include: caprylyl glycol,hexylene glycol, pentylene glycol, ethylhexylglycerin, caprylhydroxamicacid, caprylohydroxamic acid, glyceryl caprylate, and blends thereof.

Polysaccharides, such as gum Arabic, may be included as well.

Personal care compositions may comprise liquid or liquid-like carrier(s)that help to distribute, disperse, and/or dissolve the ingredients.

Non-limiting examples of suitable liquid carriers include: water,alcohols, oils, esters, and blends thereof.

The compositions of the invention may also be in the form of aqueous orhydro-alcoholic solutions.

The physiological and cosmetically acceptable medium may consistexclusively of water, a cosmetically acceptable solvent, or a blend ofwater and a cosmetically acceptable solvent, such as a lower alcoholcomposed of C1 to C4, such as ethanol, isopropanol, t-butanol,n-butanol, alkylene glycols such as propylene glycol, and glycol ethers.

In one of the embodiment, the compositions of the invention may beanhydrous.

Typically, sun care compositions may also comprise one or more UVactives, which include organic and inorganic materials that scatter,absorb, and/or reflect radiation having a wavelength from about 100 nmto about 400 nm.

In one particular embodiment, the sun care compositions protect againstUV-A, UV-B, and/or UV-C radiation.

UV-A radiation, from about 320 nm to about 400 nm, has the longestwavelengths within the UV spectrum, and consequently is the leastenergetic. UV-A radiation includes UV-A1 (from about 340 nm to about 400nm) and UV-A2 (from about 320 nm to about 340 nm). UV-B radiation hasshorter wavelengths, from about 290 nm to about 320 nm. UV-C radiationhas the shortest wavelengths from about 200 nm to about 290 nm.

In another embodiment, the sun care compositions may not contain UVactives, and may be regarded as tanning oils or tan promoters.

Sun care compositions may be formulated, for example, for application tothe lips, hair, face, cheeks, neck, area around the eyes, full hands,and body area. Self-tanning compositions, which are products that colorskin without requiring full sun exposure, also fit under the sun careumbrella.

Suitable UV absorber(s) that may be included in the personal carecompositions most likely will depend on local regulations. As the rulesgoverning the names and usage levels evolve over time, it is impossibleto include every UV absorber that may be used with the invention.

Non-limiting examples of suitable UV absorbers include: octylsalicylate; pentyl dimethyl PABA; octyl dimethyl PABA; benzophenone-1;benzophenone-6; 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol;ethyl-2-cyano-3,3-diphenylacrylate; homomenthyl salicylate;bis-ethylhexyloxyphenol methoxyphenyl triazine;methyl-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate;2-(2H-benzotriazole-2-yl)-4-methylphenol; diethylhexyl butamidotriazone; amyl dimethyl PABA; 4,6-bis(octylthiomethyl)-o-cresol; CASnumber 65447-77-0; red petroleum; ethylhexyl triazone; octocrylene;isoamyl-p-methoxycinnamate; drometrizole; titanium dioxide;2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazole-2-yl)-phenol;2-hydroxy-4-octyloxybenzophenone; benzophenone-2; diisopropylmethylcinnamate; PEG-25 PABA;2-(1,1-dimethylethyl)-6-[[3-(1,1-demethylethyl)-2-hydroxy-5-methylphenyl]methyl-4-methylphenylacrylate; drometrizole trisiloxane; menthyl anthranilate; butylmethoxydibenzoylmethane; 2-ethoxyethyl p-methoxycinnamate; benzylidenecamphor sulfonic acid; dimethoxyphenyl-[1-(3,4)]-4,4-dimethyl1,3-pentanedione; zinc oxide;N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)];pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];2,6-di-tert-butyl-4-[4,6-bis(octylthio)-1,3,5-triazin-2-ylamino]phenol;2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol;trolamine salicylate; diethylanolamine p-methoxycinnamate;polysilicone-15; CAS number 152261-33-1; 4-methylbenzylidene camphor;bisoctrizole; n-phenyl-benzenamine; reaction products with2,4,4-trimethylpentene; sulisobenzone;(2-ethylhexyl)-2-cyano-3,3-diphenylacrylate; digalloyl trioleate;polyacrylamido methylbenzylidene camphor; glyceryl ethylhexanoatedimethoxycinnamate;1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis-{[2′-cyano-bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate;benzophenone-5;1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione;hexamethylendiamine; benzophenone-8; ethyl-4-bis(hydroxypropyl)aminobenzoate;6-tert-butyl-2-(5-chloro-2H-benzotriazole-2-yl)-4-methylphenol;p-aminobenzoic acid;3,3′,3″,5,5′,5″-hexa-tert-butyl-α-α′-α″-(mesitylene-2,4,6-triyl)tri-p-cresol;lawsone with dihydroxyacetone; benzophenone-9; benzophenone-4;ethylhexyl dimethoxy benzylidene dioxoimidazoline propionate;N,N′-bisformyl-N,N′-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-;3-benzylidene camphor; terephthalylidene dicamphor sulfonic acid;camphor benzalkonium methosulfate; bisdisulizole disodium; etocrylene;ferulic acid; 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol; 4,6-bis(dodecylthiomethyl)-o-cresol;β-2-glucopyranoxy propyl hydroxy benzophenone; phenylbenzimidazolesulfonic acid; benzophenone-3; diethylamine hydroxybenzoylhexylbenzoate; 3′,3′-diphenylacryloyl)oxy]methyl}-propane; ethylhexylp-methoxycinnamate, and blends thereof.

Personal care compositions may comprise antioxidant(s) and/orantiradical protecting agent(s).

Non-limiting examples of suitable antioxidants and/or antiradicalprotecting agents include: BHA (tert-butyl-4-hydroxy anisole), BHT(2,6-di-tert-butyl-p-cresol), TBHQ (tert-butyl hydroquinone),polyphenols such as proanthocyanodic oligomers, flavonoids, hinderedamines such as tetra amino piperidine, erythorbic acid, polyamines suchas spermine, cysteine, glutathione, superoxide dismutase, lactoferrin,and blends thereof.

Personal care compositions may comprise vitamin(s), provitamin(s),and/or mineral(s).

Non-limiting examples of suitable vitamins include: ascorbic acid(vitamin C), vitamin E, vitamin E acetate, vitamin E phosphate, Bvitamins such as B3 and B5, niacin, vitamin A, derivatives thereof, andblends thereof.

Non-limiting examples of suitable provitamins include: panthenol,retinol, and blends thereof.

Non-limiting examples of suitable minerals include: talc, clay, calciumcarbonate, silica, kaolin, mica, and blends thereof. Further examples ofminerals that may be used in the personal care compositions may be foundin a brochure titled Minerals for personal care from Imerys PerformanceMinerals, the disclosure of which is hereby incorporated in its entiretyby reference.

Personal care compositions may comprise one or more surfactants.Surfactants serve in solubilizing, dispersing, emulsifying and/orreducing the interfacial tension. Surfactants may be chosen fromanionic, nonionic, amphoteric, zwitterionic, or cationic surfactants, orblends thereof.

Anionic surfactants useful herein include the water-soluble salts ofalkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical(e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonatedmonoglycerides of fatty acids having from 8 to 20 carbon atoms. Sodiumlauryl sulfate (SLS) and sodium coconut monoglyceride sulfonates arenon-limiting examples of anionic surfactants of this type.

Non-limiting examples of suitable anionic surfactants include:sarcosinates, taurates, isethionates, sodium lauryl sulfoacetate, sodiumlaureth carboxylate, and sodium dodecyl benzenesulfonate. Also suitableare alkali metal or ammonium salts of surfactants such as the sodium andpotassium salts of the following: lauroyl sarcosinate, myristoylsarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate, and oleoylsarcosinate.

Non-limiting examples of suitable cationic surfactants include:derivatives of aliphatic quaternary ammonium compounds having at leastone long alkyl chain containing from about 8 to about 18 carbon atoms,such as, lauryl trimethylammonium chloride, cetyl pyridinium chloride,cetyl trimethylammonium bromide,di-isobutylphenoxyethyl-dimethylbenzylammonium chloride, coconutalkyltrimethylammonium nitrite, cetyl pyridinium fluoride, and blendsthereof. Further suitable are quaternary ammonium fluorides havingdetergent properties such as compounds described in U.S. Pat. No.3,535,421. Certain cationic surfactants may act as germicides in thecompositions disclosed herein.

Nonionic surfactants useful herein include compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound which may be aliphatic or alkylaromatic innature.

Non-limiting examples of suitable nonionic surfactants include:poloxamers (sold under the trade name Pluronic® by BASF Corporation),polyethylene oxide condensates of alkyl phenols, products derived fromthe condensation of ethylene oxide with the reaction product ofpropylene oxide and ethylene diamine, ethylene oxide condensates ofaliphatic alcohols, long chain tertiary amine oxides, long chaintertiary phosphine oxides, long chain dialkyl sulfoxides, and blendsthereof.

Non-limiting examples of suitable zwitterionic surfactants includebetaines and derivatives of aliphatic quaternary ammonium compounds inwhich the aliphatic radicals can be straight chain or branched, andwhich contain an anionic water-solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate.

Non-limiting examples of suitable betaines include: decyl betaine or2-(N-decyl-N,N-dimethylammonio)acetate, coco betaine or2-(N-coc-N,N-dimethyl ammonio)acetate, myristyl betaine, palmitylbetaine, lauryl betaine, cetyl betaine, stearyl betaine, and blendsthereof. The amidobetaines are exemplified by cocoamidoethyl betaine,cocoamidopropyl betaine, lauramidopropyl betaine, and the like. Thebetaines of choice include cocoamidopropyl betaines such aslauramidopropyl betaine. Suitable betaine surfactants are disclosed inU.S. Pat. No. 5,180,577.

Other surfactants such as fluorinated surfactants may also beincorporated within the compositions of the invention.

Also suitable as surfactants are the following commercial products:

(1) Alkanolamides, under the trade names Amidex™ and Schercomid™;amido-amines, under the trade names Katemul™ and Schercodine™; amineoxides, under the trade names Chemoxide™ and Schercamox™; amphoterics,under the trade names Chembetaine™, Schercotaine™ and Schercoteric™;imidazolines, under the trade name Schercozoline™; pearlizing agents,under the trade name Quickpearl™; performance concentrates, under thetrade names Sulfochem™ and Chemoryl™; soaps (potassium cocoate andpotassium soyate); specialty ethoxylates, under the trade nameChemonic™; specialty quats under the trade names Quatrex™ andSchercoquat™; sulfates, under the trade name Sulfochem™; andsulfosuccinates, under the trade name Chemccinate™ from Lubrizol.

(2) Avaniel, Cremaphore®, Jordapan®, and Pluracare® from BASF Corp.

(3) Miracare® SLB, Mackam® Bab, Mackanate® Ultra SI, Miranol® Ultra, andMiracare® Plaisant from Rhodia.

(4) Stepan® Pearl 2, Stepan® Pearl 4, Stepan® Pearl Series, Neobee®M-20, Stepan® PTC, Amphosol® 2CSF, Steol®, Stepan-Mild® GCC, Stepan®SLL-FB, Stepanol® AM, Stepanol® PB, Alpha-Step® BSS-45, Bio-Terge® 804,Stepan-Mild® L3, Stepan® SLL-FB, Stepan® SSL-CG, and Stepanol® CFAS-70from Stepan Company.

Also suitable as surfactants are those described in the book Surfactantsin Personal Care Products and Decorative Cosmetics, Third Edition, 2006,CRC Press. The disclosure is incorporated hereby in its entirety byreference.

Personal care compositions may be also be formulated as detergentcompositions, such as shampoos, bath gels, and bubble baths. Suchcompositions comprise water as a liquid carrier. The surfactant orsurfactants that form the washing base may be chosen alone or in blends,from known anionic, amphoteric, zwitterionic and/or non-ionicsurfactants. The quantity and quality of the washing base must besufficient to impart a satisfactory foaming and/or detergent value tothe final composition. The washing base may be present in an amount fromabout 4% to about 50% by weight, particularly from about 6% to about 35%by weight, and more particularly from about 8% to about 25% by weight ofthe final composition.

Personal care compositions may comprise one or more thickener(s) and/orviscosifier(s).

Non-limiting examples of suitable thickeners and/or viscosifiersinclude: Acetamide MEA; acrylamide/ethalkonium chloride acrylatecopolymer; acrylamide/ethyltrimonium chloride acrylate/ethalkoniumchloride acrylate copolymer; acrylamides copolymer; acrylamide/sodiumacrylate copolymer; acrylamide/sodium acryloyldimethyltaurate copolymer;acrylates/acetoacetoxyethyl methacrylate copolymer;acrylates/beheneth-25 methacrylate copolymer; acrylates/C10-C30 alkylacrylate crosspolymer; acrylates/ceteth-20 itaconate copolymer;acrylates/ceteth-20 methacrylate copolymer; acrylates/laureth-25methacrylate copolymer; acrylates/palmeth-25 acrylate copolymer;acrylates/palmeth-25 itaconate copolymer; acrylates/steareth-50 acrylatecopolymer; acrylates/steareth-20 itaconate copolymer;acrylates/steareth-20 methacrylate copolymer; acrylates/stearylmethacrylate copolymer; acrylates/vinyl isodecanoate crosspolymer;acrylic acid/acrylonitrogens copolymer; adipic acid/methyl DEAcrosspolymer; agar; agarose; alcaligenes polysaccharides; algin; alginicacid; almondamide DEA; almondamidopropyl betaine; aluminum/magnesiumhydroxide stearate; ammonium acrylates/acrylonitrogens copolymer;ammonium acrylates copolymer; ammonium acryloyldimethyltaurate/vinylformamide copolymer; ammonium acryloyldimethyltaurate/VP copolymer;ammonium alginate; ammonium chloride; ammonium polyacryloyldimethyltaurate; ammonium sulfate; amylopectin; apricotamide DEA;apricotamidopropyl betaine; arachidyl alcohol; arachidyl glycol; arachishypogaea (peanut) flour; ascorbyl methylsilanol pectinate; astragalusgummifer gum; attapulgite; avena sativa (oat) kernel flour; avocadamideDEA; avocadamidopropyl betaine; azelamide MEA; babassuamide DEA;babassuamide MEA; babassuamidopropyl betaine; behenamide DEA; behenamideMEA; behenamidopropyl betaine; behenyl betaine; bentonite; butoxychitosan; caesalpinia spinosa gum; calcium alginate; calciumcarboxymethyl cellulose; calcium carrageenan; calcium chloride; calciumpotassium carbomer; calcium starch octenylsuccinate; C20-40 alkylstearate; canolamidopropyl betaine; capramide DEA;capryl/capramidopropyl betaine; carbomer; carboxybutyl chitosan;carboxymethyl cellulose acetate butyrate; carboxymethyl chitin;carboxymethyl chitosan; carboxymethyl dextran; carboxymethylhydroxyethylcellulose; carboxymethyl hydroxypropyl guar; carnitine;cellulose acetate propionate carboxylate; cellulose gum; ceratoniasiliqua gum; cetearyl alcohol; cetyl alcohol; cetyl babassuate; cetylbetaine; cetyl glycol; cetyl hydroxyethylcellulose; chimyl alcohol;cholesterol/HDI/pullulan copolymer; cholesteryl hexyl dicarbamatepullulan; citrus aurantium dulcis (orange) peel extract; cocamide DEA;cocamide MEA; cocamide MIPA; cocamidoethyl betaine; cocamidopropylbetaine; cocamidopropyl hydroxysultaine; coco-betaine;coco-hydroxysultaine; coconut alcohol; coco/oleamidopropyl betaine;coco-Sultaine; cocoyl sarcosinamide DEA; cornamide/cocamide DEA;cornamide DEA; croscarmellose; crosslinked bacillus/glucose/sodiumglutamate ferment; cyamopsis tetragonoloba (guar) gum; decyl alcohol;decyl betaine; dehydroxanthan gum; dextrin; dibenzylidene sorbitol;diethanolaminooleamide DEA; diglycol/CHDM/isophthalates/SIP copolymer;dihydroabietyl behenate; dihydrogenated tallow benzylmonium hectorite;dihydroxyaluminum aminoacetate; dimethicone/PEG-10 crosspolymer;dimethicone/PEG-15 crosspolymer; dimethicone propyl PG-betaine;dimethylacrylamide/acrylic acid/polystyrene ethyl methacrylatecopolymer; dimethylacrylamide/sodium acryloyldimethyltauratecrosspolymer; disteareth-100 IPDI; DMAPA acrylates/acrylicacid/acrylonitrogens copolymer; erucamidopropyl hydroxysultaine;ethylene/sodium acrylate copolymer; gelatin; gellan gum; glycerylalginate; glycine soja (soybean) flour; guar hydroxypropyltrimoniumchloride; hectorite; hyaluronic acid; hydrated silica; hydrogenatedpotato starch; hydrogenated tallow; hydrogenated tallowamide DEA;hydrogenated tallow betaine; hydroxybutyl methylcellulose; hydroxyethylacrylate/sodium acryloyldimethyl taurate copolymer;hydroxyethylcellulose; hydroxyethyl chitosan; hydroxyethylethylcellulose; hydroxyethyl stearamide-MIPA;hydroxylauryl/hydroxymyristyl betaine; hydroxypropylcellulose;hydroxypropyl chitosan; hydroxypropyl ethylenediamine carbomer;hydroxypropyl guar; hydroxypropyl methylcellulose; hydroxypropylmethylcellulose stearoxy ether; hydroxypropyl starch; hydroxypropylstarch phosphate; hydroxypropyl xanthan gum; hydroxystearamide MEA;isobutylene/sodium maleate copolymer; isostearamide DEA; isostearamideMEA; isostearamide mIPA; isostearamidopropyl betaine; lactamide MEA;lanolinamide DEA; lauramide DEA; lauramide MEA; lauramide MIPA;lauramide/myristamide DEA; lauramidopropyl betaine; lauramidopropylhydroxysultaine; laurimino bispropanediol; lauryl alcohol; laurylbetaine; lauryl hydroxysultaine; lauryl/myristyl glycol hydroxypropylether; lauryl sultaine; lecithinamide DEA; linoleamide DEA; linoleamideMEA; linoleamide MIPA; lithium magnesium silicate; lithium magnesiumsodium silicate; macrocystis pyrifera (kelp); magnesium alginate;magnesium/aluminum/hydroxide/carbonate; magnesium aluminum silicate;magnesium silicate; magnesium trisilicate; methoxy PEG-22/dodecyl glycolcopolymer; methylcellulose; methyl ethylcellulose; methylhydroxyethylcellulose; microcrystalline cellulose; milkamidopropylbetaine; minkamide DEA; minkamidopropyl betaine; MIPA-myristate;montmorillonite; Moroccan lava clay; myristamide DEA; myristamide MEA;myristamide MIPA; myristamidopropyl betaine; myristamidopropylhydroxysultaine; myristyl alcohol; myristyl betaine; natto gum;nonoxynyl hydroxyethylcellulose; oatamide MEA; oatamidopropyl betaine;octacosanyl glycol isostearate; octadecene/MA copolymer; oleamide DEA;oleamide MEA; oleamide MIPA; oleamidopropyl betaine; oleamidopropylhydroxysultaine; oleyl betaine; olivamide DEA; olivamidopropyl betaine;oliveamide MEA; palmamide DEA; palmamide MEA; palmamide MIPA;palmamidopropyl betaine; palmitamide DEA; palmitamide MEA;palmitamidopropyl betaine; palm kernel alcohol; palm kernelamide DEA;palm kernelamide MEA; palm kernelamide MIPA; palm kernelamidopropylbetaine; peanutamide MEA; peanutamide MIPA; pectin; PEG-800;PEG-crosspolymer; PEG-150/decyl alcohol/SMDI copolymer; PEG-175diisostearate; PEG-190 distearate; PEG-15 glyceryl tristearate; PEG-140glyceryl tristearate; PEG-240/HDI copolymer bis-decyltetradeceth-20ether; PEG-100/IPDI copolymer; PEG-180/laureth-50/™MG copolymer;PEG-10/lauryl dimethicone crosspolymer; PEG-15/lauryl dimethiconecrosspolymer; PEG-2M; PEG-5M; PEG-7M; PEG-9M; PEG-14M; PEG-20M; PEG-23M;PEG-25M; PEG-45M; PEG-65M; PEG-90M; PEG-115M; PEG-160M; PEG-180M;PEG-120 methyl glucose trioleate; PEG-180/octoxynol-40/™MG copolymer;PEG-150 pentaerythrityl tetrastearate; PEG-4 rapeseedamide;PEG-150/stearyl alcohol/SMDI copolymer; phaseolus angularis seed powder;polianthes tuberosa extract; polyacrylate-3; polyacrylic acid;polycyclopentadiene; polyether-1; polyethylene/isopropyl maleate/MAcopolyol; polyglyceryl-3 disiloxane dimethicone; polyglyceryl-3polydimethylsiloxyethyl dimethicone; polymethacrylic acid;polyquaternium-52; polyvinyl alcohol; potassium alginate; potassiumaluminum polyacrylate; potassium carbomer; potassium carrageenan;potassium chloride; potassium palmate; potassium polyacrylate; potassiumsulfate; potato starch modified; PPG-2 cocamide; PPG-1 hydroxyethylcaprylamide; PPG-2 hydroxyethyl cocamide; PPG-2 hydroxyethylcoco/isostearamide; PPG-3 hydroxyethyl soyamide; PPG-14 laureth-60 hexyldicarbamate; PPG-14 laureth-60 isophoryl dicarbamate; PPG-14 palmeth-60hexyl dicarbamate; propylene glycol alginate; PVP/decene copolymer; PVPmontmorillonite; pyrus cydonia seed; pyrus malus (apple) fiber;rhizobian gum; ricebranamide DEA; ricinoleamide DEA; ricinoleamide MEA;ricinoleamide MIPA; ricinoleamidopropyl betaine; ricinoleic acid/adipicacid/AEEA copolymer; rosa multiflora flower wax; sclerotium gum;sesamide DEA; sesamidopropyl betaine; sodium acrylate/acryloyldimethyltaurate copolymer; sodium acrylates/acrolein copolymer; sodiumacrylates/acrylonitrogens copolymer; sodium acrylates copolymer; sodiumacrylates crosspolymer; sodium acrylate/sodium acrylamidomethylpropanesulfonate copolymer; sodium acrylates/vinyl isodecanoate crosspolymer;sodium acrylate/vinyl alcohol copolymer; sodium carbomer; sodiumcarboxymethyl chitin; sodium carboxymethyl dextran; sodium carboxymethylbeta-glucan; sodium carboxymethyl starch; sodium carrageenan; sodiumcellulose sulfate; sodium chloride; sodium cyclodextrin sulfate; sodiumhydroxypropyl starch phosphate; sodium isooctylene/MA copolymer; sodiummagnesium fluorosilicate; sodium oleate; sodium palmitate; sodium palmkernelate; sodium polyacrylate; sodium polyacrylate starch; sodiumpolyacryloyldimethyl taurate; sodium polygamma-glutamate; sodiumpolymethacrylate; sodium polystyrene sulfonate; sodium silicoaluminate;sodium starch octenylsuccinate; sodium stearate; sodium stearoxyPG-hydroxyethylcellulose sulfonate; sodium styrene/acrylates copolymer;sodium sulfate; sodium tallowate; sodium tauride acrylates/acrylicacid/acrylonitrogens copolymer; sodium tocopheryl phosphate; solanumtuberosum (potato) starch; soyamide DEA; soyamidopropyl betaine;starch/acrylates/acrylamide copolymer; starch hydroxypropyltrimoniumchloride; stearamide AMP; stearamide DEA; stearamide DEA-distearate;stearamide DIBA-stearate; stearamide MEA; stearamide MEA-stearate;stearamide MIPA; stearamidopropyl betaine; steareth-60 cetyl ether;steareth-100/PEG-136/HDI copolymer; stearyl alcohol; stearyl betaine;sterculia urens gum; synthetic fluorphlogopite; tallamide DEA; tallowalcohol; tallowamide DEA; tallowamide MEA; tallowamidopropyl betaine;tallowamidopropyl hydroxysultaine; tallowamine oxide; tallow betaine;tallow dihydroxyethyl betaine; tamarindus indica seed gum; tapiocastarch; TEA-alginate; TEA-carbomer; TEA-hydrochloride; trideceth-2carboxamide MEA; tridecyl alcohol; triethylene glycol dibenzoate;trimethyl pentanol hydroxyethyl ether; triticum vulgare (wheat) germpowder; triticum vulgare (wheat) kernel flour; triticum vulgare (wheat)starch; tromethamine acrylates/acrylonitrogens copolymer; tromethaminemagnesium aluminum silicate; undecyl alcohol; undecylenamide DEA;undecylenamide MEA; undecylenamidopropyl betaine; welan gum; wheatgermamide DEA; wheat germamidopropyl betaine; xanthan gum; yeastbeta-glucan; yeast polysaccharides; zea mays (corn) starch; and blendsthereof.

Also suitable as thickeners and/or viscosifiers are the followingcommercial products:

(1) Aqualon™ carboxymethylcellulose, Benecel™ methylcellulose andhydroxypropyl methylcellulose, Blanose™ sodium carboxymethylcellulose,Klucel™ hydroxypropylcellulose, Natrosol™ hydroxyethylcellulose,Natrosol™ Plus and PolySurf™ cetyl modified hydroxyethylcellulose,n-Hance™ cationic guar, n-Hance™ HP Series hydroxypropyl guar, n-Hance™SP-100 conditioning polymer, and Supercol™ guar gum from AshlandSpecialty Ingredients

(2) Carbopol® Polymers, Fixate™ PLUS Polymer, Glucamate™ Thickeners,Amidex™ Surfactants, Chembetaine™ Surfactants, Chemoxide™ Surfactants,Chemonic™ Surfactants, Chemccinate™ Surfactants, Amidex™ BC-24Surfactant, Chemoryl™ LB-30 Surfactant, Novethix™ L-10 Polymer, Ceralan™Lanolin Product, Pemulen™ TR-1 Polymeric Emulsifier, Pemulen™ TR-2Polymeric Emulsifier, Hydramol™ PGPD Ester, Schercodine™ M Amido-Amine,Schercodine™ P Amido-Amine, Schercomid™ Diethanolamides from TheLubrizol Corporation.

(3) Salcare® and Luvigel® from BASF Corporation.

(4) Aculyn™ 22, Aculyn™ 28, Aculyn™ 33, Aculyn™ 38, and Aculyn™ 44 fromThe Dow Chemical Company.

(5) Ammonyx® C and Stepan-Mild® GCC from Stepan Company.

(6) Stabileze™, Rapithix™ A-60, Rapithix™ A-100, Ultrathix™ P-100,Lubrajel™ and FlexiThix™ from Ashland Specialty Ingredients (Wayne,N.J.).

Also suitable as a thickener/rheology modifier are lightly- tomoderately-crosslinked polyvinylpyrrolidones. Disclosures of thesepolymers are provided in the following publications, each of which ishereby incorporated in its entirety by reference: U.S. Pat. Nos.5,073,614; 5,312,619; 5,139,770; 5,716,634; 5,470,884; 5,759,524;5,997,887; 6,024,942; as well as international applicationPCT/US10/26973, PCT/US10/26976, PCT/US10/26940, PCT/US11/32993, andPCT/US11/34515.

Personal care compositions may comprise natural extracts and/or naturalproducts. Extensive details on natural products that can be used inpersonal care compositions is provided in book chapter “Chemistry ofCosmetics, Comprehensive Natural Products II” in Chemistry and Biology;volume 3, 2010.

Oral Care Composition Ingredients

Oral care compositions may optionally contain one or more additionalingredients. Non-limiting examples of suitable ingredients include:carriers, dentifrices, cleaning agents, breath freshening actives, painrelievers, anesthetics, anti-inflammatory agents, antimicrobial agents,antibacterial agents, anti-calculus agents, anti-plaque agents, gums,thickeners, gelling agents, surfactants, flavors, warming or tinglingagents, tooth bleaching agents, whiteners, stain removers, stainpreventers, abrasives, adhesives, colors, emollients, emulsifiers,preservatives, solvents, binders, stimulants, depressants, diet aids,smoking cessation aides, vitamins, minerals, throat-soothing agents,spices, herbs, herbal extracts, alkaloids (such as caffeine andnicotine), and humectants.

The choice of a carrier to be used is basically determined by the waythe composition is to be introduced into the oral cavity. Carriermaterials for toothpaste, tooth gel or the like include abrasivematerials, sudsing agents, binders, humectants, flavoring and sweeteningagents, as disclosed in e.g., U.S. Pat. No. 3,988,433. Carrier materialsfor biphasic dentifrice formulations are disclosed in U.S. Pat. Nos.5,213,790; 5,145,666; 5,281,410; 4,849,213; and 4,528,180. Mouthwash,rinse or mouth spray carrier materials typically include water,flavoring and sweetening agents, etc., as disclosed in, e.g., U.S. Pat.No. 3,988,433. Lozenge carrier materials typically include a candy base;chewing gum carrier materials include a gum base, flavoring andsweetening agents, as in, e.g., U.S. Pat. No. 4,083,955. Sachet carriermaterials typically include a sachet bag, flavoring and sweeteningagents. For sub-gingival gels used for delivery of actives into theperiodontal pockets or around the periodontal pockets, a “sub-gingivalgel carrier” is chosen as disclosed in, e.g., U.S. Pat. Nos. 5,198,220and 5,242,910. The selection of a carrier will depend on secondaryconsiderations like taste, cost, and shelf stability, and other factors.

Oral care compositions may comprise one or more dental abrasives. Dentalabrasives useful in the compositions include many different materials.The material selected must be one which is compatible within thecomposition of interest and does not excessively abrade dentin.

Non-limiting examples of suitable abrasives include: silicas includinggels and precipitates, insoluble sodium polymetaphosphate, hydratedalumina, calcium carbonate, dicalcium orthophosphate dihydrate, calciumpyrophosphate, tricalcium phosphate, calcium polymetaphosphate, resinousabrasive materials such as particulate condensation products of urea andformaldehyde, and blends thereof.

Another class of abrasives is the particulate thermo-setting polymerizedresins as described in U.S. Pat. No. 3,070,510.

Non-limiting examples of suitable resins include: melamines, phenolics,ureas, melamine-ureas, melamine-formaldehydes, urea-formaldehyde,melamine-urea-formaldehydes, cross-linked epoxides, cross-linkedpolyesters, and blends thereof.

Silica dental abrasives of various types may be employed because oftheir unique benefits of exceptional dental cleaning and polishingperformance without unduly abrading tooth enamel or dentine. The silicaabrasive polishing materials herein, as well as other abrasives,generally have an average particle size ranging from about 0.1 to about30 microns, and particularly from about 5 to about 15 microns. Theabrasive can be precipitated silica or silica gels such as the silicaxerogels described in U.S. Pat. No. 3,538,230, and U.S. Pat. No.3,862,307.

Non-limiting examples of suitable silica abrasives include: silicaxerogels marketed under the trade name “Syloid” by the W.R. Grace &Company, Davison Chemical Division and precipitated silica materialssuch as those marketed by the J.M. Huber Corporation under the tradename, Zeodent®, particularly the silicas carrying the designationZeodent® 119, Zeodent® 118, Zeodent® 109 and Zeodent® 129. The types ofsilica dental abrasives useful in the toothpastes of the invention aredescribed in more detail in U.S. Pat. Nos. 4,340,583; 5,603,920;5,589,160; 5,658,553; 5,651,958; and 6,740,311. Each of thesedisclosures is hereby incorporated in its entirety by reference.

Mixtures of abrasives can be used such as mixtures of the various gradesof Zeodent® silica abrasives listed above.

The total amount of abrasive(s) in the oral care compositions typicallyrange from about 6% to about 70% by weight; toothpastes may contain fromabout 10% to about 50% of abrasives by weight of the composition. Dentalsolution, mouth spray, mouthwash and non-abrasive gel compositionstypically contain little or no abrasives.

Oral care compositions may comprise polymeric mineral surface activeagent(s) (PMSAs). PMSAs include any agent which will have a strongaffinity for the tooth surface, deposit a polymer layer or coating onthe tooth surface and produce the desired surface modification effects.The “mineral” descriptor is intended to convey that the surface activityor substantivity of the polymer is toward mineral surfaces such ascalcium phosphate minerals or teeth.

Non-limiting examples of suitable PMSAs include: polyelectrolytes suchas condensed phosphorylated polymers; polyphosphonates; copolymers ofphosphate- or phosphonate-containing monomers or polymers with othermonomers such as ethylenically unsaturated monomers and amino acids orwith other polymers such as proteins, polypeptides, polysaccharides,poly(acrylate), poly(acrylamide), poly(methacrylate), poly(ethacrylate),poly(hydroxyalkylmethacrylate), poly(vinyl alcohol), poly(maleicanhydride), poly(maleate) poly(amide), poly(ethylene amine),poly(ethylene glycol), poly(propylene glycol), poly(vinyl acetate),poly(vinyl benzyl chloride), polycarboxylates, carboxy-substitutedpolymers, and blends thereof. Also suitable as polymeric mineral surfaceactive agents are the carboxy-substituted alcohol polymers described inU.S. Pat. Nos. 5,292,501; 5,213,789, 5,093,170; 5,009,882; and4,939,284; and the diphosphonate-derivatized polymers in U.S. Pat. No.5,011,913; the synthetic anionic polymers including polyacrylates andcopolymers of maleic anhydride or acid and methyl vinyl ether (e.g.,Gantrez®), as described, for example, in U.S. Pat. No. 4,627,977.Another example of a polymeric mineral surface active agent is adiphosphonate modified polyacrylic acid.

Polymers with activity must have sufficient surface binding propensityto desorb pellicle proteins and remain affixed to enamel surfaces. Fortooth surfaces, polymers with end or side chain phosphate or phosphonatefunctions may be used, although other polymers with mineral bindingactivity may prove effective depending upon adsorption affinity.

PMSAs are useful in the compositions because of their stain preventionbenefit. It is believed the PMSAs provide a stain prevention benefitbecause of their reactivity or substantivity to mineral surfaces,resulting in desorption of portions of undesirable adsorbed pellicleproteins, in particular those associated with binding color bodies thatstain teeth, calculus development and attraction of undesirablemicrobial species. The retention of these PMSAs on teeth can alsoprevent stains from accruing due to disruption of binding sites of colorbodies on tooth surfaces.

The ability of PMSA to bind stain promoting ingredients of oral careproducts such as stannous ions and cationic antimicrobials is alsobelieved to be helpful. The PMSA will also provide tooth surfaceconditioning effects which produce desirable effects on surfacethermodynamic properties and surface film properties, which impartimproved clean feel aesthetics both during and most importantly,following rinsing or brushing. Many of these polymeric agents are alsoknown or expected to provide tartar control benefits when applied inoral compositions, hence providing improvement in both the appearance ofteeth and their tactile impression to consumers. The desired surfaceeffects may include: 1) creating a hydrophilic tooth surface immediatelyafter treatment; and 2) maintaining surface conditioning effects andcontrol of pellicle film for extended periods following product use,including post brushing or rinsing and throughout more extended periods.The effect of creating an increased hydrophilic surface can be measuredin terms of a relative decrease in water contact angles. The hydrophilicsurface, importantly, is maintained on the tooth surface for an extendedperiod after using the product.

Oral care compositions may comprise additional anticalculus agent(s),such as a pyrophosphate salt as a source of pyrophosphate ion.

Non-limiting examples of suitable pyrophosphate salts include: dialkalimetal pyrophosphate salts, tetraalkali metal pyrophosphate salts, andmixtures thereof. Particularly, disodium dihydrogen pyrophosphate(Na₂H₂P₂O₇), tetrasodium pyrophosphate (Na₄P₂O₇), and tetrapotassiumpyrophosphate (K₄P₂O₇) in their unhydrated as well as hydrated forms mayfind utility.

In compositions of the invention, the pyrophosphate salt may be presentin one of three ways: predominately dissolved, predominatelyundissolved, or a mixture of dissolved and undissolved pyrophosphate.

Compositions comprising predominately dissolved pyrophosphate refer tocompositions where at least one pyrophosphate ion source is in an amountsufficient to provide at least about 1.0% free pyrophosphate ions. Theamount of free pyrophosphate ions may be from about 1% to about 15%,particularly from about 1.5% to about 10%, and more particularly fromabout 2% to about 6%. Free pyrophosphate ions may be present in avariety of protonated states depending on the pH of the composition.

Compositions comprising predominately undissolved pyrophosphate refer tocompositions containing no more than about 20% of the totalpyrophosphate salt dissolved in the composition, particularly less thanabout 10% of the total pyrophosphate dissolved in the composition.Tetrasodium pyrophosphate salt may be one such pyrophosphate salt inthese compositions. Tetrasodium pyrophosphate may be the anhydrous saltform or the decahydrate form, or any other species stable in solid formin the oral care compositions. The salt is in its solid particle form,which may be its crystalline and/or amorphous state, with the particlesize of the salt being small enough to be aesthetically acceptable andreadily soluble during use. The amount of pyrophosphate salt useful inmaking these compositions is any tartar control effective amount,generally from about 1.5% to about 15%, particularly from about 2% toabout 10%, and more particularly from about 3% to about 8% by weight ofthe oral care composition.

The pyrophosphate salts are described in more detail in Kirk-OthmerEncyclopedia of Chemical Technology, third edition, volume 17,Wiley-Interscience Publishers (1982).

Oral care compositions may comprise peroxide compounds.

Non-limiting examples of suitable peroxide compounds include: hydrogenperoxide and organic peroxides including urea peroxide, carbamideperoxide, glyceryl peroxide, benzoyl peroxide, derivatives thereof, andblends thereof.

Typically, the peroxide compound can be employed in amounts so that atleast about 1% by weight of the composition comprises peroxide. Theperoxide compound may comprise from about 2% to about 30% by weight ofthe composition. More particularly, the peroxide comprises from about 3%to about 15% by weight of the composition. A typical peroxideconcentration in the composition is generally from about 2% to about 7%by weight for home use products, and from about 15% to about 20% byweight for dental professional use.

Thickening or gelling agents used in dentifrice compositions may includenonionic polyoxyethylene polyoxypropylene block copolymers. Illustrativeof polyoxyethylene polyoxypropylene block copolymers useful in thepractice include block copolymers having the formulaHO(C₂H₄O)_(b)(C₃H₆O₆)_(a)(C₂H₄O)_(b)H wherein a is an integer such thatthe hydrophobic base represented by (C₃H₆O₆) has a molecular weight ofabout 2,750 Da to 4000 Da, b is an integer such that the hydrophilicportion (moiety) represented by (C₂H₄O) constitutes from about 70% toabout 80% by weight of the copolymer. Block copolymers of thiscomposition are available commercially under the trademark Pluronic® Ftype.

Pluronic® F127 has a molecular weight of 4,000 Da and contains 70% ofthe hydrophilic polyoxyethylene moiety.

Also suitable as a thickening agent is lightly- tomoderately-crosslinked PVP, described in international applicationPCT/US11/30642.

The thickening agents may be present in an amount from about 15% toabout 50% by weight, particularly from about 25% to about 45% by weightof the composition.

Surfactants may also be included in the oral care compositions of theinvention, where they may serve in solubilizing, dispersing, emulsifyingand/or reducing the surface tension of the teeth in order to increasethe contact between the tooth and the peroxide. The compositions mayalso comprise surfactants, also commonly referred to as sudsing agents.Suitable surfactants are those which are reasonably stable and foamthroughout a wide pH range. Surfactants may be chosen from anionic,nonionic, amphoteric, zwitterionic, or cationic surfactants, or blendsthereof.

Anionic surfactants useful herein include the water-soluble salts ofalkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical(e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonatedmonoglycerides of fatty acids having from 8 to 20 carbon atoms. Sodiumlauryl sulfate (SLS) and sodium coconut monoglyceride sulfonates arenon-limiting examples of anionic surfactants of this type. Many suitableanionic surfactants are disclosed in U.S. Pat. No. 3,959,458. Thecompositions may comprise an anionic surfactant in an amount from about0.025% to about 9% by weight, particularly from about 0.05% to about 5%by weight, and more particularly from about 0.1% to about 1% by weightof the composition.

Non-limiting examples of suitable anionic surfactants include:sarcosinates, taurates, isethionates, sodium lauryl sulfoacetate, sodiumlaureth carboxylate, and sodium dodecyl benzenesulfonate. Also suitableare alkali metal or ammonium salts of surfactants such as the sodium andpotassium salts of the following: lauroyl sarcosinate, myristoylsarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate, and oleoylsarcosinate. The sarcosinate surfactant may be present in thecompositions from about 0.1% to about 2.5%, particularly from about 0.5%to about 2.0% by weight of the total composition.

Non-limiting examples of suitable cationic surfactants include:derivatives of aliphatic quaternary ammonium compounds having at leastone long alkyl chain containing from about 8 to about 18 carbon atomssuch as lauryl trimethylammonium chloride, cetyl pyridinium chloride,cetyl trimethylammonium bromide,di-isobutylphenoxyethyl-dimethylbenzylammonium chloride, coconutalkyltrimethylammonium nitrite, cetyl pyridinium fluoride, and blendsthereof. Also suitable are the quaternary ammonium fluorides describedin U.S. Pat. No. 3,535,421, where the quaternary ammonium fluorides havedetergent properties. Certain cationic surfactants can also act asgermicides in the compositions disclosed herein.

Nonionic surfactants that may be used in the compositions of theinvention include compounds produced by the condensation of alkyleneoxide groups (hydrophilic in nature) with an organic hydrophobiccompound which may be aliphatic or alkylaromatic in nature.

Non-limiting examples of suitable nonionic surfactants include:poloxamers (sold under the trade name Pluronic® by BASF Corporation),polyethylene oxide condensates of alkyl phenols, products derived fromthe condensation of ethylene oxide with the reaction product ofpropylene oxide and ethylene diamine, ethylene oxide condensates ofaliphatic alcohols, long chain tertiary amine oxides, long chaintertiary phosphine oxides, long chain dialkyl sulfoxides and blendsthereof.

Non-limiting examples of suitable zwitterionic surfactants includebetaines and derivatives of aliphatic quaternary ammonium compounds inwhich the aliphatic radicals can be straight chain or branched, andwhich contain an anionic water-solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate, or phosphonate.

Non-limiting examples of suitable betaines include: decyl betaine or2-(N-decyl-N,N-dimethylammonio)acetate, coco betaine or2-(N-coc-N,N-dimethyl ammonio)acetate, myristyl betaine, palmitylbetaine, lauryl betaine, cetyl betaine, stearyl betaine, and blendsthereof. The amidobetaines are exemplified by cocoamidoethyl betaine,cocoamidopropyl betaine, lauramidopropyl betaine, and the like. Thebetaines of choice include cocoamidopropyl betaines such aslauramidopropyl betaine. Suitable betaine surfactants are disclosed inU.S. Pat. No. 5,180,577.

Other surfactants such as fluorinated surfactants may also beincorporated within the compositions of the invention.

Oral care compositions may comprise flavor(s).

Non-limiting examples of suitable flavors include: methyl salicylate,ethyl salicylate, methyl cinnamate, ethyl cinnamate, butyl cinnamate,ethyl butyrate, ethyl acetate, methyl anthranilate, iso-amyl acetate,iso-amyl butyrate, allyl caproate, eugenol, eucalyptol, thymol, cinnamicalcohol, cinnamic aldehyde, octanol, octanal, decanol, decanal,phenylethyl alcohol, benzyl alcohol, benzaldehyde, α-terpineol,linalool, limonene, citral, vanillin, ethyl vanillin, propenyl guaethol,maltol, ethyl maltol, heliotropin, anethole, dihydroanethole, carvone,oxanone, menthone, β-damascenone, ionone, gamma decalactone, gammanonalactone, gamma undecalactone, 4-hydroxy-2,5-dimethyl-3(2H)-furanone,and blends thereof.

Generally suitable flavoring agents are those containing structuralfeatures and functional groups that are less prone to oxidation byperoxide. These include derivatives of flavor chemicals that aresaturated or contain stable aromatic rings or ester groups.

Also suitable are flavor chemicals that may undergo some oxidation ordegradation without resulting in a significant change in the flavorcharacter or profile. The flavor chemicals, including menthol, may beprovided as single or purified chemicals rather than supplied in thecomposition by addition of natural oils or extracts such as peppermint,spearmint, or wintergreen oils as these sources may contain othercomponents that are relatively unstable and may degrade in the presenceof peroxide. Flavoring agents are generally used in the compositions atlevels of from about 0.001% to about 5% by weight of the composition.

The flavor system may typically include sweetening agent(s). Sweetenersinclude compounds of natural and artificial origin.

Non-limiting examples of suitable water-soluble natural sweetenersinclude: monosaccharides, disaccharides and polysaccharides, such asxylose, ribose, glucose (dextrose), mannose, galactose, fructose(levulose), sucrose (sugar), maltose, invert sugar (a mixture offructose and glucose derived from sucrose), partially hydrolyzed starch,corn syrup solids, dihydrochalcones, monellin, steviosides,glycyrrhizin, and blends thereof.

Non-limiting examples of suitable water-soluble artificial sweetenersinclude: soluble saccharin salts, i.e., sodium or calcium saccharinsalts, cyclamate salts, the sodium, ammonium or calcium salt of3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide, the potassiumsalt of 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide(acesulfame-K), the free acid form of saccharin, and the like. Othersuitable sweeteners include dipeptide based sweeteners, such asL-aspartic acid derived sweeteners, such as L-aspartyl-L-phenylalaninemethyl ester (aspartame) and materials described in U.S. Pat. No.3,492,131,L-α-aspartyl-N-(2,2,4,4-tetramethyl-3-thietanyl)-D-alaninamide hydrate,methyl esters of L-aspartyl-L-phenylglycerin andL-aspartyl-L-2,5,dihydrophenyl-glycine,L-aspartyl-2,5-dihydro-L-phenylalanine,L-aspartyl-L-(1-cyclohexyen)-alanine, derivatives thereof, and blendsthereof. Water-soluble sweeteners derived from naturally occurringwater-soluble sweeteners, such as a chlorinated derivative of ordinarysugar (sucrose), known, for example, under the product description ofsucralose as well as protein based sweeteners such as thaumatoccousdanielli (Thaumatin I and II) may be used. The compositions may containsweetener(s) in an amount from about 0.1% to about 10% by weight, inparticular from about 0.1% to about 1% by weight of the composition.

In addition, the flavor system may include salivating agents, warmingagents, and numbing agents. These agents are present in the compositionsin an amount from about 0.001% to about 10% by weight, particularly fromabout 0.1% to about 1% by weight of the composition.

A non-limiting example of suitable salivating agent includes Jambus®manufactured by Takasago. Non-limiting examples of suitable warmingagents include capsicum and nicotinate esters such as benzyl nicotinate.Non-limiting examples of suitable numbing agents include benzocaine,lidocaine, clove bud oil, ethanol, and blends thereof.

Oral care compositions may comprise chelating agent(s).

The chelating agents may include metal solubilizing agents and metalprecipitating agents. The metal solubilizing agents include a condensedpyrophosphate compound. For purposes of this invention “condensedphosphate” relates to an inorganic phosphate composition containing twoor more phosphate species in a linear or cyclic pyrophosphate form. Thecondensed phosphate may be sodium pyrophosphate, but may also includetripolyphosphate, hexametaphosphate, cyclic condensed phosphate or othersimilar phosphates well known in the field. The blend may also includean organic chelating agent. The term “organic phosphate” includesphosphonic acid, di and tri phosphonoc acid compound or its salts. Anexample of phosphonic acid is 1-hydroxyethylidene-1,1-diphosphonic acidthat is sold under the trade name of Dequest®. The blend may alsoinclude a metal precipitating chelating agent. The term “metalprecipitating chelating agent” is an agent that binds to metals andcauses the metal to precipitate and includes halogens such as fluoride.The chelating agents are incorporated in the oral care compositions ofthe invention in an amount from about 0.1% to about 8.0% by weight, andparticularly from about 0.5% to about 3.0% by weight of the composition,in a ratio of about 3:1:1 w/w organic chelating agent: condensedphosphate chelating agent: metal precipitating agent.

Another optional ingredient that may be used in oral care compositionsis a humectant. For example, a humectant may be added to keep toothpastecompositions from hardening upon exposure to air, to give compositions amoist feel to the mouth, and, for particular humectants, to impartdesirable sweetness of flavor to toothpaste compositions. The humectant,on a pure humectant basis, is generally present from about 0% to about70%, particularly from about 5% to about 25% by weight of thecomposition.

Non-limiting examples of suitable humectants include: edible polyhydricalcohols such as glycerin, sorbitol, xylitol, butylene glycol,polyethylene glycol, propylene glycol, trimethyl glycine, and blendsthereof.

The invention also contemplates oral care compositions comprisingpolymer(s) described herein complexed with hydrogen peroxide. Adescription of such complexes is present in international application WO91/07184, the contents of which are hereby incorporated in theirentirety by reference.

Also contemplated are oral care compositions such as those described inthe following patents and patent applications, the contents of each arehereby incorporated in their entirety by reference: WO 2011/068514, WO2011/053877, US 2010/0275394, US 2011/0076090, US 2008/091935, US2008/0181716, US 2008/0014224, WO 2007/066837, US 2008/0292669, US2007/0071696, US 2007/0154863, US 2008/0317797, US 2005/0249678, US2007/0178055, US 2007/0189983, WO 2005/041910, U.S. Pat. No. 7,785,572,WO 1998/005749, WO 1997/022651, and U.S. Pat. No. 5,310,563.

Oral care compositions may comprise one or more denture adhesives.

Synthetic materials presently dominate the denture adhesive market. Suchmaterials may consist of mixtures of the salts of short-acting polymers(e.g., carboxymethylcellulose or “CMC”) and long-acting polymers (e.g.,poly[vinyl methyl ether maleate], or “Gantrez” and its salts).Polyvinylpyrrolidone (povidone) may also be used.

Other components of denture adhesive products impart particular physicalattributes to the formulations. Petrolatum, mineral oil, andpolyethylene oxide may be included in creams to bind the materials andto make their placement easier. Silicon dioxide and calcium stearate maybe used in powders to minimize clumping. Menthol and peppermint oils maybe used for flavoring, red dye for color, and sodium borate and methyl-or poly-paraben as preservatives.

It is also contemplated that the composition ingredients may beformulated in a single container, or the ingredients may be formulatedin-part in two or more distinct containers of the same or differenttype, the contents of which may require mixing prior to use.

The UV-absorbing polymers according to the invention may be preparedaccording to the examples set out below. The examples are presented forpurposes of demonstrating, but not limiting, the preparation of thecompounds, polymers, and non-homopolymers according to the invention.

EXAMPLES Example 1 Poly(IB/MA) Grafted with JT Benzone, Half Ethyl Esterand Sodium Salt Forms

A premix was prepared having 0.8 g (3.25 mM) of JT benzone and 1.1 g(3.25 mM) NaOEt/EtOH, and then 1.0 7 of ethanol was added with stirringuntil the premix was thoroughly dissolved. Then, 5.0 g ofpoly(isobutylene-co-maleic anhydride) having a weight-average molecularweight (M_(w)) of 80,000 Da was added and the mixture heated to 135° C.for 10 hours. Afterward, the mixture was cooled to room temperature toobtain a clear dark yellow ethanol solution that was also soluble inethanol/water solutions and oils, such di-isopropyl-adipate. The molarquantities are such that a=b+c+d.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 2 Poly(IB/MA) Grafted with JT Benzone and Isobutylamine; HalfEthyl Ester, Amic Acid, and Imide Forms

Example 1 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 3 Poly(IB/MA) Grafted with JT Benzone and n-Octylamine; HalfEthyl Ester, Amic Acid, Full Imide and Sodium Salt Forms

Example 2 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 4 Poly(IB/MA) Grafted with JT Benzone and n-Dodecylamine; HalfEthyl Ester, Amic Acid, Full Imide and Sodium Salt Forms

Example 2 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 5 Poly(IB/MA) Grafted with JT Benzone andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, Full Imide andSodium Salt Forms

Example 2 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution was obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Examples 6-10 Poly(IB/MA) Grafted with JT Benzone, Lower MolecularWeight Variants

Examples 1-5 are substantially repeated, in each case the poly(IB/MA)copolymer having a M_(w) of 80,000 Da is replaced with the samecopolymer having a M_(w) of 6,000 Da. A clear dark yellow ethanolsolution is obtained that is also soluble in ethanol/water solutions andother alcohols.

These products may be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 11 Poly(MVE/MA) Grafted with HE-JT Benzone; Half Ethyl Ester andSodium Salt Forms

Example 1 was substantially repeated, replacing the poly(IB/MA)copolymer having a M_(w) of 80,000 Da with a copolymer of methyl vinylether and maleic anhydride having a M_(w) of 130,000 Da, and replacingthe JT benzone with 0.94 g (3.25 mM) of HE-JT benzone. The clear,dark-colored product in ethanol solution was soluble in ethanol/watersolutions and in oils like di-isopropyl adipate. The molar quantitiesare such that a=b+c+d.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 12 Poly(MVE/MA) Grafted with HE-JT Benzone and Isobutylamine;Half Ethyl Ester, Amic Acid, Full Imide and Sodium Salt Forms

Example 11 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which is dissolved with 6.0 gethanol. The molar quantities are such that a=b+c+d+e+f.

This product may be used for personal care gels/emulsions for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B Skinsunscreen applications.

Example 13 Poly(MVE/MA) Grafted with HE-JT Benzone and n-Octylamine;Half Ethyl Ester, Amic Acid, Full Imide and Sodium Salt Forms

Example 11 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, which is dissolved with 6.0 gethanol. The product is cooled to room temperature to obtain a cleardark colored ethanol solution that is soluble in alcohols and in oilslike di-isopropyl-adipate or coconut oil. The molar quantities are suchthat a=b+c+d+e+f.

This product may be used for personal care gels/emulsions for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 14 Poly(MVE/MA) Grafted with HE-JT Benzone and n-Dodecylamine;Half Ethyl Ester, Amic Acid, Full Imide and Sodium Salt Forms

Example 11 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, which is dissolved with 6.0 gethanol. The product is cooled to room temperature to obtain a cleardark colored ethanol solution that is soluble in alcohols and in oilslike di-isopropyl-adipate or coconut oil. The molar quantities are suchthat a=b+c+d+e+f.

This product may be used for personal care gels/emulsions for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 15 Poly(MVE/MA) Grafted with HE-JT Benzone andDimethylaminopropylamine; Half Ethyl Ester, Full Imide and Sodium SaltForms

Example 11 is substantially repeated, except 3.3 g (26 mM) ofn-dodecylamine is added to the premix, which was dissolved with 9.0 gethanol. The product is cooled to room temperature to obtain a cleardark colored ethanol solution that is soluble in alcohols and in oilslike di-isopropyl-adipate or coconut oil. The molar quantities are suchthat a=b+c+d+e+f.

This product may be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Examples 16-20 Poly(MVE/MA) Grafted with HE-JT Benzone, Lower MolecularWeight Variants

Examples 11-15 were substantially repeated, except the poly(MVE/MA)copolymer having a M_(w) of 130,000 Da was replaced by an equal amountof the same copolymer having a M_(w) of 2,500 Da. The products werecooled to room temperature to obtain clear dark colored ethanolsolutions that was soluble in alcohols and in oils likedi-isopropyl-adipate or coconut oil.

These products may be used for personal care formulations for hairand/or skin applications.

Example 21 Poly(Octadecene/MA) Grafted with HE-JT Benzone

Example 11 was substantially repeated, replacing the poly(MVE/MA)copolymer having a Mw of 130,000 Da with a copolymer of octadecene andmaleic anhydride having a Mw of 6,000 Da. Instead of ethanol, 24 g ofcetyl alcohol was used to dissolve the HE-JT benzone, to which thecopolymer was added and heated to 135° C. for 10 hours. The product wascooled to room temperature to obtain a creamy solid that was miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 22 Poly(Octadecene/MA) Grafted with HE-JT Benzone andIsobutylamine, Amic Acid and Full Imide Forms

Example 21 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the HE-JT benzone and the cetyl alcohol. Theproduct was cooled to room temperature to obtain a creamy solid that wasmiscible in ethanol/water solutions and soluble in oils likedi-isopropyl-adipate. The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 23 Poly(Octadecene/MA) Grafted with HE-JT Benzone andn-Octylamine, Amic Acid and Full Imide Forms

Example 22 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine replaced isobutylamine. The product was cooled to roomtemperature to obtain a creamy solid that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

Example 24 Poly(Octadecene/MA) Grafted with HE-JT Benzone andn-Dodecylamine, Amic Acid and Full Imide Forms

Example 22 was substantially repeated, except 1.9 g (26 mM) ofn-dodecylamine replaced isobutylamine. The product was cooled to roomtemperature to obtain a creamy solid that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e.

Example 25 Poly(Octadecene/MA) Grafted with HE-JT Benzone andDimethylaminopropylamine, Amic Acid and Full Imide Forms

Example 22 was substantially repeated, except 2.7 g (26 mM) ofdimethylpropylamine replaced isobutylamine. The product was cooled toroom temperature to obtain a creamy solid that was miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 26 Poly(Styrene/MA) Grafted with HE-JT Benzone

Example 21 was substantially repeated, replacing thepoly(octadecene/maleic anhydride) copolymer having a M_(w) of 6,000 Dawith a copolymer of styrene and maleic anhydride having a M_(w) of 6,000Da, and replacing the JT benzone with 0.94 g (3.25 mM) of HE-JT benzone.The product was cooled to room temperature to obtain a creamy solid thatwas soluble in ethanol solutions and soluble in oils likedi-isopropyl-adipate. The molar quantities are such that a=b+c.

This product can be used for personal care gels/emulsions for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 27 Poly(Styrene/MA) Grafted with HE-JT Benzone and Isobutylene,Amic Acid and Full Imide Forms

Example 26 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the HE-JT benzone and the cetyl alcohol. Theproduct was cooled to room temperature to obtain a creamy solid that wassoluble in ethanol solutions and soluble in oils likedi-isopropyl-adipate. The molar quantities are such that a=b+c+d+e.

This product can be used for personal care gels/emulsions for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 28 Poly(Styrene/MA) Grafted with HE-JT Benzone and n-Octylamine,Amic Acid and Full Imide Forms

Example 26 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine replaced to isobutylene. The product was cooled to roomtemperature to obtain a creamy solid that was soluble in ethanolsolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e.

This product can be used for personal care gels/emulsions for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 29 Poly(Styrene/MA) Grafted with HE-JT Benzone andn-Dodecylamine, Amic Acid and Full Imide Forms

Example 26 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine replaced to isobutylene. The product was cooled to roomtemperature to obtain a creamy solid that was soluble in ethanolsolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e.

This product can be used for personal care gels/emulsions for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 30 Poly(Styrene/MA) Grafted with HE-JT Benzone andDimethylaminopropylamine, Amic Acid and Full Imide Forms

Example 26 was substantially repeated, except 4.8 g (26 mM) ofdimethylaminopropylamine replaced to isobutylene. The product was cooledto room temperature to obtain a creamy solid that was soluble in ethanolsolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 31 Poly(Styrene/MA) Grafted with JT Benzone

Example 26 was substantially repeated, except 0.8 g (3.25 mM) ofJT-benzone replaced the HE-JT benzone. The product was cooled to roomtemperature to obtain a creamy solid that was soluble in ethanolsolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 32 Poly(Styrene/MA) Grafted with JT Benzone and Isobutylamine,Amic Acid and Full Imide Forms

Example 31 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the mixture with JT benzone and the cetylalcohol. The product was cooled to room temperature to obtain a creamysolid that was soluble in ethanol solutions and soluble in oils likedi-isopropyl-adipate. The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 33 Poly(Styrene/MA) Grafted with JT Benzone and n-Octylamine,Amic Acid and Full Imide Forms

Example 31 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine replaced the isobutylamine. The product was cooled to roomtemperature to obtain a creamy solid that was soluble in ethanolsolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 34 Poly(Styrene/MA) Grafted with JT Benzone and n-Dodecylamine,Amic Acid and Full Imide Forms

Example 31 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine replaced the isobutylamine. The product was cooled toroom temperature to obtain a creamy solid that was soluble in ethanolsolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 35 Poly(Styrene/MA) Grafted with JT Benzone andDimethylaminopropylamine, Amic Acid and Full Imide Forms

Example 31 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine replaced the isobutylamine. The product wascooled to room temperature to obtain a creamy solid that was soluble inethanol solutions and soluble in oils like di-isopropyl-adipate. Themolar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 36 Poly(IB/MA) Grafted with 577-Sulfanamide-Propylenediamine,Half Ethyl Ester, Amic Acid, and Full Imide Forms

A premix was prepared having 1.2 g (3.25 mM)577-sulfanamide-propylenediamine and 7 g ethanol until the UV active wasthoroughly dissolved. Then, 5.0 g of poly(isobutylene-co-maleicanhydride) having a weight-average molecular weight (M_(w)) of 80,000 Dawas added and the mixture heated to 135° C. for 10 hours. Afterward, themixture was cooled to room temperature to obtain a clear dark yellowethanol solution that was also soluble in ethanol/water solutions andoils, such di-isopropyl-adipate. The molar quantities are such thata=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 37 Poly(IB/MA) Grafted with 577-Sulfanamide-Propylenediamine andIsobutylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 36 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 38 Poly(IB/MA) Grafted with 577-Sulfanamide-Propylenediamine andn-Octylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 36 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 39 Poly(IB/MA) Grafted with 577-Sulfanamide-Propylenediamine andn-Dodecylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 36 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 40 Poly(IB/MA) Grafted with 577-Sulfanamide-Propylenediamine andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 36 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution was obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 41 Poly(IB/MA) Grafted with 577-Sulfanamide-Ethanolamine, HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 36 was substantially repeated, replacing the 1.2 g (3.25 mM) of577-sulfanamide-propylenediamine with 1.15 g (3.25 mM) of577-sulfanamide-ethanolamine. The product mixture was cooled to roomtemperature to obtain a clear dark yellow ethanol solution that was alsosoluble in ethanol/water solutions and oils, such di-isopropyl-adipate.The molar quantities are such that a=b+c+d.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 42 Poly(IB/MA) Grafted with 577-Sulfanamide-Ethanolamine andIsobutylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 41 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product may be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 43 Poly(IB/MA) Grafted with 577-Sulfanamide-Ethanolamine andn-Octylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 41 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product may be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 44 Poly(IB/MA) Grafted with 577-Sulfanamide-Ethanolamine andn-Dodecylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 41 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f.

This product may be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 45 Poly(IB/MA) Grafted with 577-Sulfanamide-Ethanolamine andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 41 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution is obtainedthat is also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f.

This product may be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 46 Poly(IB/MA) Grafted with 577-Sulfanamide-Hexylenediamine,Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 36 was substantially repeated, replacing the 1.2 g (3.25 mM) of577-sulfanamide-propylenediamine with 1.15 g (3.25 mM) of577-sulfanamide-hexylenediamine. The product mixture was cooled to roomtemperature to obtain a clear dark yellow ethanol solution that was alsosoluble in ethanol/water solutions and oils, such di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 47 Poly(IB/MA) Grafted with 577-Sulfanamide-Hexylenediamine andIsobutylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 46 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 48 Poly(IB/MA) Grafted with 577-Sulfanamide-Hexylenediamine andn-Octylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 46 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 49 Poly(IB/MA) Grafted with 577-Sulfanamide-Hexylenediamine andn-Dodecylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 46 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 50 Poly(IB/MA) Grafted with 577-Sulfanamide-Hexylenediamine andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 46 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution was obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Examples 51-55 Poly(IB/MA) Grafted with577-Sulfanamide-Propylenediamine, Lower Molecular Weight Variants

Examples 36-40 were substantially repeated, replacing the poly(IB/MA)having a M_(w) of 80,000 Da by the same copolymer having a M_(w) of6,000 Da.

Examples 56-60 Poly(IB/MA) Grafted with 577-Sulfanamide-Hexylenediamine,Lower Molecular Weight Variants

Examples 46-50 are substantially repeated, replacing the poly(IB/MA)having a M_(w) of 80,000 Da by the same copolymer having a M_(w) of6,000 Da.

Examples 61-65 Poly(IB/MA) Grafted with 577-Sulfanamide-Ethanolamine,Lower Molecular Weight Variants

Examples 41-45 are substantially repeated, replacing the poly(IB/MA)having a M_(w) of 80,000 Da by the same copolymer having a M_(w) of6,000 Da.

Example 66 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamine,Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 36 is substantially repeated, replacing the poly(IB/MA)copolymer with an equal amount of poly(methyl vinyl ether/MA) having aM_(w) of 130,000 Da. The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 67 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand Isobutylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 66 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 68 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand n-Octylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 66 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 69 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand n-Dodecylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 66 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 70 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand Dimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and FullImide Forms

Example 66 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution is obtainedthat is also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Examples 71-75 Poly(MVE/MA) Grafted with577-Sulfanamide-Propylenediamine, Higher Molecular Weight Variants

Examples 66-70 are substantially repeated, replacing the poly(MVE/MA)having a M_(w) of 130,000 Da by the same copolymer having a M_(w) of2,500,000 Da.

Example 76 Poly(Octadecene/MA) Grafted with577-Sulfanamide-Propylenediamine; Half Ethyl Ester, Amic Acid, and FullImide Forms

Example 66 was substantially repeated, replacing the poly(MVE/MA) havinga M_(w) of 130,000 Da by the copolymer of octadecene and maleicanhydride having a M_(w) of 6,000 Da. Cetyl alcohol (17 g) was usedinstead of ethanol. A creamy solid was obtained that was miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 77 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand Isobutylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 76 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A creamy solid was obtained that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 78 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand n-Octylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 76 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A creamy solid was obtained that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 79 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand n-Dodecylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 76 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A creamy solid was obtained that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 80 Poly(MVE/MA) Grafted with 577-Sulfanamide-Propylenediamineand Dimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and FullImide Forms

Example 76 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A creamy solid was obtained that was miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 81 Poly(Styrene/MA) Grafted with577-Sulfanamide-Propylenediamine; Half Ethyl Ester, Amic Acid, and FullImide Forms

Example 66 was substantially repeated, replacing the poly(styrene/MA)having a M_(w) of 130,000 Da by the copolymer of octadecene and maleicanhydride having a M_(w) of 6,000 Da. Cetyl alcohol (17 g) was usedinstead of ethanol. A creamy solid was obtained that was miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 82 Poly(Styrene/MA) Grafted with577-Sulfanamide-Propylenediamine and Isobutylamine; Half Ethyl Ester,Amic Acid, and Full Imide Forms

Example 81 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A creamy solid was obtained that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 83 Poly(Styrene/MA) Grafted with577-Sulfanamide-Propylenediamine and n-Octylamine; Half Ethyl Ester,Amic Acid, and Full Imide Forms

Example 81 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A creamy solid was obtained that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 84 Poly(Styrene/MA) Grafted with577-Sulfanamide-Propylenediamine and n-Dodecylamine; Half Ethyl Ester,Amic Acid, and Full Imide Forms

Example 81 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A creamy solid was obtained that was miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 85 Poly(Styrene/MA) Grafted with577-Sulfanamide-Propylenediamine and Dimethylaminopropylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 81 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A creamy solid was obtained that was miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 86 Poly(Styrene/MA) Grafted with577-Sulfanamide-Hexylenediamine; Half Ethyl Ester, Amic Acid, and FullImide Forms

Example 66 is substantially repeated, replacing the poly(styrene/MA)having a M_(w) of 130,000 Da by the copolymer of octadecene and maleicanhydride having a M_(w) of 6,000 Da. Cetyl alcohol (17 g) is usedinstead of ethanol. A creamy solid is obtained that is miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 87 Poly(Styrene/MA) Grafted with 577-Sulfanamide-Hexylenediamineand Isobutylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 86 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which is dissolved with 6.0 gethanol. A creamy solid is obtained that is miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 88 Poly(Styrene/MA) Grafted with 577-Sulfanamide-Hexylenediamineand n-Octylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 86 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, and it is dissolved with 6.0 gethanol. A creamy solid is obtained that is miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 89 Poly(Styrene/MA) Grafted with 577-Sulfanamide-Hexylenediamineand n-Dodecylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 86 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it is dissolved with 6.0 gethanol. A creamy solid is obtained that is miscible in ethanol/watersolutions and soluble in oils like di-isopropyl-adipate. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations for UV-A/Bprotection for hair and as a styling agent, and for UV-A/B suncareapplications.

Example 90 Poly(Styrene/MA) Grafted with 577-Sulfanamide-Hexylenediamineand Dimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and FullImide Forms

Example 86 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A creamy solid is obtained that is miscible inethanol/water solutions and soluble in oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 91 Poly(IB/MA) Grafted with DMABPD, Half Ethyl Ester, Amic Acid,and Full Imide Forms

Example 46 was substantially repeated, replacing the 1.2 g (3.25 mM) of577-sulfanamide-hexylenediamine with 0.71 g (3.25 mM) of DMABPD. Theproduct mixture was cooled to room temperature to obtain a clear darkyellow ethanol solution that was also soluble in ethanol/water solutionsand oils, such di-isopropyl-adipate. The molar quantities are such thata=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 92 Poly(IB/MA) Grafted with DMABPD and Isobutylamine; Half EthylEster, Amic Acid, and Full Imide Forms

Example 91 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 93 Poly(IB/MA) Grafted with DMABPD and n-Octylamine; Half EthylEster, Amic Acid, and Full Imide Forms

Example 91 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 94 Poly(IB/MA) Grafted with DMABPD and n-Dodecylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 91 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 95 Poly(IB/MA) Grafted with DMABPD and Dimethylaminopropylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 91 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution was obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 96 Poly(IB/MA) Grafted with DMABHD, Half Ethyl Ester, Amic Acid,and Full Imide Forms

Example 46 is substantially repeated, replacing the 1.2 g (3.25 mM) of577-sulfanamide-hexylenediamine with 0.71 g (3.25 mM) of DMABHD. Theproduct mixture is cooled to room temperature to obtain a clear darkyellow ethanol solution that is also soluble in ethanol/water solutionsand oils, such di-isopropyl-adipate. The molar quantities are such thata=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 97 Poly(IB/MA) Grafted with DMABHD and Isobutylamine; Half EthylEster, Amic Acid, and Full Imide Forms

Example 96 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 98 Poly(IB/MA) Grafted with DMABHD and n-Octylamine; Half EthylEster, Amic Acid, and Full Imide Forms

Example 96 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 99 Poly(IB/MA) Grafted with DMABHD and n-Dodecylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 96 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 100 Poly(IB/MA) Grafted with DMABHD andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 96 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution is obtainedthat is also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 101 Poly(IB/MA) Grafted with DMABEA, Half Ethyl Ester, AmicAcid, and Full Imide Forms

Example 46 is substantially repeated, replacing the 1.2 g (3.25 mM) of577-sulfanamide-hexylenediamine with 0.71 g (3.25 mM) of DMABEA. Theproduct mixture is cooled to room temperature to obtain a clear darkyellow ethanol solution that is also soluble in ethanol/water solutionsand oils, such di-isopropyl-adipate. The molar quantities are such thata=b+c+d.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 102 Poly(IB/MA) Grafted with DMABEA and Isobutylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 101 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 103 Poly(IB/MA) Grafted with DMABEA and n-Octylamine; Half EthylEster, Amic Acid, and Full Imide Forms

Example 101 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 104 Poly(IB/MA) Grafted with DMABEA and n-Dodecylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 101 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 105 Poly(IB/MA) Grafted with DMABEA andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 101 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution is obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Examples 106-110 Poly(IB/MA) Grafted with DMABPD, Lower Molecular WeightVariants

Examples 91-95 were substantially repeated, in each case the poly(IB/MA)copolymer having a M_(w) of 80,000 Da was replaced with the samecopolymer having a M_(w) of 6,000 Da. A clear dark yellow ethanolsolution was obtained that was also soluble in ethanol/water solutionsand other alcohols.

Examples 110-115 Poly(IB/MA) Grafted with DMABEA, Higher MolecularWeight Variants

Examples 91-95 were substantially repeated, in each case the poly(IB/MA)copolymer having a M_(w) of 6,000 Da was replaced with the samecopolymer having a M_(w) of 80,000 Da. A clear dark yellow ethanolsolution was obtained that was also soluble in ethanol/water solutionsand other alcohols.

Example 116 Poly(MVE/MA) Grafted with DMABPD, Half Ethyl Ester, AmicAcid, and Full Imide Forms

Example 91 was substantially repeated, replacing the poly(IB/MA)copolymer with a copolymer of methyl vinyl ether and maleic anhydridehaving a M_(w) of 130,000 Da. The product mixture was cooled to roomtemperature to obtain a clear dark yellow ethanol solution that was alsosoluble in ethanol/water solutions and oils, such di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 117 Poly(MVE/MA) Grafted with DMABPD and Isobutylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 116 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 118 Poly(MVE/MA) Grafted with DMABPD and n-Octylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 116 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 119 Poly(MVE/MA) Grafted with DMABPD and n-Dodecylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 116 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 120 Poly(MVE/MA) Grafted with DMABPD andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 116 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution was obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 121 Poly(MVE/MA) Grafted with DMABEA, Half Ethyl Ester, AmicAcid, and Full Imide Forms

Example 116 was substantially repeated, replacing DMABPD with 0.67 g(3.25 mM) of DMABEA, and replacing the poly(MVE/MA) copolymer having aM_(w) of 130,000 Da with the same copolymer having a M_(w) of 2,500,000Da. The product mixture was cooled to room temperature to obtain a cleardark yellow ethanol solution that was also soluble in ethanol/watersolutions and oils, such di-isopropyl-adipate. The molar quantities aresuch that a=b+c+d.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 122 Poly(MVE/MA) Grafted with DMABEA and Isobutylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 121 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 123 Poly(MVE/MA) Grafted with DMABEA and n-Octylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 121 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 124 Poly(MVE/MA) Grafted with DMABEA and n-Dodecylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 121 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 125 Poly(MVE/MA) Grafted with DMABEA andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 121 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution is obtainedthat is also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 126 Poly(Octadecene/MA) Grafted with DMABPD, Half Ethyl Ester,Amic Acid, and Full Imide Forms

Example 116 was substantially repeated, replacing the poly(MVE/MA)copolymer with a copolymer of octadecene and maleic anhydride having aM_(w) of 6,000 Da. Cetyl alcohol (24 g) was used instead of ethanol. Theproduct mixture was cooled to room temperature to obtain a clear darkyellow ethanol solution that was also soluble in ethanol/water solutionsand oils, such di-isopropyl-adipate. The molar quantities are such thata=b+c+d.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 127 Poly(Octadecene/MA) Grafted with DMABPD and Isobutylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 126 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 128 Poly(Octadecene/MA) Grafted with DMABPD and n-Octylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 126 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 129 Poly(Octadecene/MA) Grafted with DMABPD and n-Dodecylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 126 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 130 Poly(Octadecene/MA) Grafted with DMABPD andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 126 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution was obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 131 Poly(Octadecene/MA) Grafted with DMABEA, Half Ethyl Ester,Amic Acid, and Full Imide Forms

Example 126 is substantially repeated, replacing DMABPD with 0.67 g(3.25 mM) DMABEA. Cetyl alcohol (24 g) is used instead of ethanol. Theproduct mixture is cooled to room temperature to obtain a clear darkyellow ethanol solution that is also soluble in ethanol/water solutionsand oils, such di-isopropyl-adipate. The molar quantities are such thata=b+c.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 132 Poly(Octadecene/MA) Grafted with DMABEA and Isobutylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 131 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 133

Poly(Octadecene/MA) Grafted with DMABEA and n-Octylamine; Half EthylEster, Amic Acid, and Full Imide Forms

Example 131 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 134 Poly(Octadecene/MA) Grafted with DMABEA and n-Dodecylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 131 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 135 Poly(Octadecene/MA) Grafted with DMABEA andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 131 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution is obtainedthat is also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 136 Poly(Styrene/MA) Grafted with DMABEA, Half Ethyl Ester, AmicAcid, and Full Imide Forms

Example 131 is substantially repeated, replacing poly(octadecene/MA)with the copolymer of styrene and maleic anhydride having M_(w) of 6,000Da. Cetyl alcohol (24 g) is used instead of ethanol. The product mixtureis cooled to room temperature to obtain a clear dark yellow ethanolsolution that is also soluble in ethanol/water solutions and oils, suchdi-isopropyl-adipate. The molar quantities are such that a=b+c.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 137 Poly(Styrene/MA) Grafted with DMABEA and Isobutylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 136 is substantially repeated, except 1.9 g (26 mM) ofisobutylamine is added to the premix, which is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 138 Poly(Styrene/MA) Grafted with DMABEA and n-Octylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 137 is substantially repeated, except 3.3 g (26 mM) ofn-octylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 139 Poly(Styrene/MA) Grafted with DMABEA and n-Dodecylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 137 is substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine is added to the premix, and it is dissolved with 6.0 gethanol. A clear dark yellow ethanol solution is obtained that is alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 140 Poly(Styrene/MA) Grafted with DMABEA andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 137 is substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine is added to the premix, and it is dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution is obtainedthat is also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 141 Poly(Styrene/MA) Grafted with DMABPD, Half Ethyl Ester, AmicAcid, and Full Imide Forms

Example 136 was substantially repeated, replacing DMABEA with 0.71 g(3.25 mM) of DMABPD. Cetyl alcohol (24 g) was used instead of ethanol.The product mixture was cooled to room temperature to obtain a cleardark yellow ethanol solution that was also soluble in ethanol/watersolutions and oils, such di-isopropyl-adipate. The molar quantities aresuch that a=b+c+d.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 142 Poly(Styrene/MA) Grafted with DMABPD and Isobutylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 141 was substantially repeated, except 1.9 g (26 mM) ofisobutylamine was added to the premix, which was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 143 Poly(Styrene/MA) Grafted with DMABPD and n-Octylamine; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 141 was substantially repeated, except 3.3 g (26 mM) ofn-octylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate.The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 144 Poly(Styrene/MA) Grafted with DMABPD and n-Dodecylamine;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 141 was substantially repeated, except 4.8 g (26 mM) ofn-dodecylamine was added to the premix, and it was dissolved with 6.0 gethanol. A clear dark yellow ethanol solution was obtained that was alsosoluble in ethanol/water solutions and oils like di-isopropyl-adipate,or coconut, vegetable, or soybean oil. The molar quantities are suchthat a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 145 Poly(Styrene/MA) Grafted with DMABPD andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 141 was substantially repeated, except 2.7 g (26 mM) ofdimethylaminopropylamine was added to the premix, and it was dissolvedwith 9.0 g ethanol. A clear dark yellow ethanol solution was obtainedthat was also soluble in ethanol/water solutions and other alcohols. Themolar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for conditioning hair and/or skinapplications.

Example 146 Poly(Styrene/MA) Grafted with JT Benzone and DMABEA; HalfEthyl Ester, Amic Acid, and Full Imide Forms

Example 101 is substantially repeated, reacting 0.8 g (3.25 mM) of JTbenzone and 0.71 g (3.25 mM) of DMABEA with 1.1 g (3.25 mM) NaOH/EtOHand 5.0 g of poly(isobutylene-co-maleic anhydride) have a M_(w) of80,000 Da. A clear dark yellow ethanol solution is obtained that also issoluble in ethanol/water solutions and other alcohols. The molarquantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 147 Poly(MVE/MA) Grafted with HE-JT Benzone, DMABEA andIsobutylamine; Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 12 is substantially repeated, adding 0.71 g (3.25 mM) of DMABEAto the reactive mixture and removing the sodium ethanol. A clear darkyellow ethanol solution is obtained that also is soluble inethanol/water solutions and other alcohols. The molar quantities aresuch that a=b+c+d+e+f+g+h.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 148 Poly(IB/MA) Grafted with Sulfanamide-PD and HE-JT Benzone;Half Ethyl Ester, Amic Acid, and Full Imide Forms

Example 36 is substantially repeated, adding 0.94 g (3.25 mM) of HE-JTbenzone to the reactive mixture. A clear dark yellow ethanol solution isobtained that also is soluble in ethanol/water solutions and otheralcohols. The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 149 Poly(MVE/MA) Grafted with Sulfanamide-EA, HE-JT Benzone, andDimethylaminopropylamine; Half Ethyl Ester, Amic Acid, and Full ImideForms

Example 75 is substantially repeated, replacing the 1.2 g (3.25 mM) of577-sulfanamide-propylenediamine with 1.15 g (3.25 mM) of577-sulfanamide-ethanolamine, and adding 0.94 g (3.25 mM) of HE-JTbenzone to the reactive mixture. A clear dark yellow ethanol solution isobtained that also is soluble in ethanol/water solutions and otheralcohols. The molar quantities are such that a=b+c+d+e+f+g.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and skin as a conditioningagent, and for UV-A/B suncare applications.

Example 150 Poly(IB/MA) Grafted with JT Benzone andMethyl-2-Aminobenzoate; Amic Acid, Imide, Half Ethyl Ester and SodiumSalt Forms

Example 1 is substantially repeated, adding 0.49 g (3.25 mM)methyl-2-aminobenzoate to the reactive mix. A clear dark yellow ethanolsolution is obtained that also is soluble in ethanol/water solutions andother alcohols. The molar quantities are such that a=b+c+d+e+f.

This product can be used for personal care formulations, such asgels/emulsions for UV-A/B protection for hair and as a styling agent,and for UV-A/B suncare applications.

Example 151 Poly(MVE/MA) Grafted with DMABPD, Methyl-2-Aminobenzoate,and 2-Aminobenzophenone; Half Ethyl Ester, Amic Acid, Imide, and SodiumSalt Forms

Example 116 is substantially repeated, adding 0.49 g (3.25 mM)methyl-2-aminobenzoate and 0.64 g (3.25 mM) 2-aminobenzophenone to thereactive mix. A clear dark yellow ethanol solution is obtained that alsois soluble in ethanol/water solutions and other alcohols. The molarquantities are such that a=b+c+d+e+f+g+h+i.

Example 152 Poly(IB/MA) Grafted with DIOPAT, Dimethylaminopropylamine;Full Imide Form

A 1-L, 4-neck round-bottom flask was charged with ethanol (250 mL), 37.5g 2,4-bis-(2,4-dihydroxyphenyl)-6-(4-methoxyphenyl)-s-triazine (DIOPAT)and 85.0 g (0.657 mol) of dimethylaminopropylamine, and a yellow-goldslurry formed with mixing. A KOH/water solution was then added thatformed a loose light orange mixture after one hour of mixing. Duringthis time, the reaction temperature increased from 25 to 30° C. A doughysample was collected and submitted for ₁HNMR analysis. The balance ofthe product was collected from the flask and charged to a PARR reactor.The PARR heating schedule was programmed to ramp from 25° C. to 100° C.in 30 min. Temperature was held at 100° C. for 3 hours, ramped to 145°C. and held at 145° C. for 4 hours. Finally, the reactor was cooled to50° C. and maintained over night. The next morning, the product wasdischarged as 200 g total solids. The solids were charged to a cleanPARR reactor with 500 mL ethanol. The reactor was twice-purged withpressurized nitrogen which swept oxygen from the reactor to eliminateamine-oxide formation. A gold-colored liquid was discharged from thereactor. The solvent was stripped at 70° C. and the viscous liquidpoured into a Pyrex dish and heated in a vacuum oven at 70-80° C. toobtain a vacuum dried solid.

Example 153 Other DIOPAT-Grafted Polymers

Example 152 is substantially repeated to create other product lines.First, poly(IB/MA) is grafted with DIOPAT and dimethylaminopropylamineis replaced by at least one other hydrophobic grafting reactant (e.g.,n-butylamine, iso-butylamine, n-octylamine, tert-octylamide, and/orn-dodecylamine). Second, poly(IB/MA) is replaced by other polymershaving at least one anhydride moiety [e.g., poly(MVE/MA),poly(styrene/MA), of varying weight-average molecular weights], which isused for the grafting reaction comprising DIOPAT and other hydrophobicgrafting reactant(s) (e.g., dimethylaminopropylamine, n-butylamine,iso-butylamine, n-octylamine, tert-octylamide, and/or n-dodecylamine).

What is claimed is:
 1. A polymer comprising: a first repeating unitselected from the group consisting of:

and combinations thereof, and wherein each Z is a residue of a monomerindependently selected from the group consisting of functionalized andunfunctionalized: alpha-olefins is selected from the group consistingof: isobutylene, octadecene, and combinations thereof; each X isindependently selected from the group consisting of O, NR₁, andcombinations thereof; each R₁ and R₂ is independently selected from thegroup consisting of hydrogen, halogen, and functionalized andunfunctionalized hydrocarbyl optionally having one or more heteroatoms;each R₃ is independently selected from the group consisting of hydrogen,U, and functionalized and unfunctionalized hydrocarbyl optionally havingone or more heteroatoms; each M is independently selected from the groupconsisting of alkali metal ion, alkaline earth metal ion, ammonium ion,and combinations thereof; each U has a structure independently selectedfrom the group consisting of:

and combinations thereof, wherein each R₃₁, R₃₂, R₃₃, R₃₄, R₃₅, R₄₁,R₄₂, R₄₃, R₄₄ and R₄₅ is independently selected from the groupconsisting of hydrogen, halogen, amino, alkyl amino, hydroxyl, alkoxyl,sulfonyl, carboxyl, functionalized and unfunctionalized hydrocarbyloptionally having one or more heteroatoms, and combinations thereof;each Y is independently selected from the group consisting of O, NR₁, S,and combinations thereof; each Q is independently selected from thegroup consisting of functionalized and unfunctionalized hydrocarbyleneoptionally having one or more heteroatoms; and each

(wavy bond) indicates the point of attachment for each said U.
 2. Thepolymer according to claim 1 wherein each said U has a structureindependently selected from the group consisting of:

and combinations thereof, wherein each

(wavy bond) indicates the point of attachment for each said U.
 3. Thepolymer according to claim 1 having a structure selected from the groupconsisting of:

wherein b, c, d, e, f, g, and h are mole fractions such that sum of saidmole fractions for each said polymer equals to 1.0.